NOCB-NLKW-PS-chemical Bonding

Unit 4
CHEMiCAL BOnDinG AnD

MOLECULAR StRUCtURE
Scientists are constantly discovering new compounds,

orderly arranging the facts about them, trying to explain
with the existing knowledge, organising to modify the
earlier views or evolve theories for explaining the newly
After studying this Unit, you will be observed facts.
able to
• understand Kössel-Lewis
approach to chemical bonding;
• explain the octet rule and its Matter is made up of one or different type of elements.
limitations, draw Lewis structures Under normal conditions no other element exists as an
of simple molecules; independent atom in nature, except noble gases. However,
• explain the formation of different a group of atoms is found to exist together as one species
types of bonds; having characteristic properties. Such a group of atoms
is called a molecule. Obviously there must be some force
• describe the VSEPR theory and
which holds these constituent atoms together in the
predict the geometry of simple
molecules. the attractive force which holds various
molecules; offs
constituents (atoms, ions, etc.) together in different
• explain the valence bond to To
chemical species is called a chemical bond. Since the
TEAR
gig
approach for the formation of
formation of chemical compounds takes place as a result of
covalent bonds;
combination of atoms of various elements in different ways,
• predict the directional properties it raises many questions. Why do atoms combine? Why are
of covalent bonds; only certain combinations possible? Why do some atoms
• explain the different types of
combine while certain others do not? Why do molecules
hybridisation involving s, p and possess definite shapes? To answer such questions different
d orbitals and draw shapes of theories and concepts have been put forward from time
simple covalent molecules; to time. These are Kössel-Lewis approach, Valence Shell
Electron Pair Repulsion (VSEPR) Theory, Valence Bond (VB)
• describe the molecular orbital
theory of homonuclear diatomic Theory and Molecular Orbital (MO) Theory. The evolution
molecules; of various theories of valence and the interpretation of
the nature of chemical bonds have closely been related to
• explain the concept of hydrogen
the developments in the understanding of the structure
bond.
of atom, the electronic configuration of elements and the
periodic table. Every system tends to be more stable and
bonding is nature’s way of lowering the energy of the system
to attain stability.
Rationalised 2023-24
ChemiCal Bonding and moleCular StruCture 101
4.1 KÖ S S E L - L E w i S A p p R O A C H t O the number of valence electrons. This number

CHEMiCAL BOnDinG of valence electrons helps to calculate the
common or group valence of the element.
In order to explain the formation of chemical D o
g .ME
bond in terms of electrons, a number of The group valence of the elements is generally
attempts were made, but it was only in either equal to the number of dots in Lewis
symbols or 8 minus the number of dots or
1916 when Kössel and Lewis succeeded ff
valence electrons.
independently in giving a satisfactory
explanation. They were the first to provide Kössel, in relation to chemical bonding,
some logical explanation of valence which was drew attention to the following facts:
based on the inertness of noble gases. • In the periodic table, the highly
electronegative halogens and the highly
Lewis pictured the atom in terms of a Masse
electropositive alkali metals are separated
away
positively charged ‘Kernel’ (the nucleus plus
the inner electrons) and the outer shell that by the noble gases;
could accommodate a maximum of eight • The formation of a negative ion from a
electrons. He, further assumed that these se halogen atom and a positive ion from
eight electrons occupy the corners of a cube an alkali metal atom is associated with
the gain and loss of an electron by the
which surround the ‘Kernel’. Thus the single
outer shell electron of sodium would occupy
Bee Bee
respective atoms;
one corner of the cube, while in the case of • The negative and positive ions thus
a noble gas all the eight corners would be formed attain stable noble gas electronic
occupied. This octet of electrons, represents configurations. The noble gases (with the
a particularly stable electronic arrangement. exception of helium which has a duplet
Lewis postulated that atoms achieve
Teams Easy
of electrons) have a particularly stable
to
the stable octet when they are linked by
To
outer shell configuration of eight (octet)
chemical bonds. In the case of sodium and
chlorine, this can happen by the transfer of page
electrons, ns2np6.
• The negative and positive ions are stabilized
an electron from sodium to chlorine thereby by electrostatic attraction.
as
t as
ME
giving the Na+ and Cl– ions. In the case of
other molecules like Cl2, H2, F2, etc., the bond For example, the formation of NaCl from
is formed by the sharing of a pair of electrons sodium and chlorine, according to the above
scheme, can be explained as:
between the atoms. In the process each atom
attains a stable outer octet of electrons. Na → Na+ + e–
Lewis Symbols: In the formation of a [Ne] 3s1 [Ne]
molecule, only the outer shell electrons take Cl + e– → Cl–
part in chemical combination and they are [Ne] 3s 3p
2 5
[Ne] 3s2 3p6 or [Ar]
3ft A
Footage
known as valence electrons. The inner shell
electrons are well protected and are generally
Na+ + Cl– → NaCl or Na+Cl–
not involved in the combination process. Similarly the formation of CaF2 may be
G.N. Lewis, an American chemist introduced shown as:
Ca → Ca2+ + 2e–
simple notations to represent valence electrons
in an atom. These notations are called Lewis [Ar]4s2
Egs
[Ar]
symbols. For example, the Lewis symbols for F + e– → F–
the elements of second period are as under:
[He] 2s2 2p5 [He] 2s2 2p6 or [Ne]
→
ooo a
of 3 Mrs
Ca2+ + 2F– CaF2 or Ca2+(F– )2
the bond formed, as a result of the
Significance of Lewis Symbols : The electrostatic attraction between the
number of dots around the symbol represents positive and negative ions was termed as
102 chemistry
the electrovalent bond. the electrovalence chlorine atoms attain the outer shell octet of
INTENSE
is thus equal to the number of unit charge(s) the nearest noble gas (i.e., argon).
oases
on the ion. Thus, calcium is assigned a
positive electrovalence of two, while chlorine
a negative electrovalence of one.
they
the dots represent electrons. Such
structures are referred to as Lewis dot
a
Kössel’s postulations provide the basis for
structures.
The Lewis dot structures can be written for
the modern concepts regarding ion-formation
other molecules also, in which the combining
by electron transfer and the formation of ionic
atoms may be identical or different. The
crystalline compounds. His views have proved
important conditions being that:
to be of great value in the understanding and
• Each bond is formed as a result of sharing
systematisation of the ionic compounds. At
of an electron pair between the atoms.to
the same time he did recognise the fact that Most
• Each combining atom contributes at least
a large number of compounds did not fit into
one electron to the shared pair.
these concepts. Eero Eggsy
• The combining atoms attain the outer-
4.1.1 Octet Rule
shell noble gas configurations as a result
Kössel and Lewis in 1916 developed an of the sharing of electrons.
important theory of chemical combination
• Thus in water and carbon tetrachloride
between atoms known as electronic theory
molecules, formation of covalent bonds
of chemical bonding. According to this,
can be represented as:
atoms can combine either by transfer of
valence electrons from one atom to another
te
(gaining or losing) or by sharing of valence
Teat
3g in order to have an octet in their
electrons
valence shells. This is known as octet rule.
4.1.2 Covalent Bond

Langmuir (1919) refined the Lewis
postulations by abandoning the idea of
the stationary cubical arrangement of the
octet, and by introducing the term covalent
bond. The Lewis-Langmuir theory can be thus, when two atoms share one
understood by considering the formation of electron pair they are said to be joined by
a single covalent bond. In many compounds
the chlorine molecule, Cl2. The Cl atom with
electronic configuration, [Ne]3s2 3p5, is one
Isa
we have multiple bonds between atoms. The
teas
electron short of the argon configuration. formation of multiple bonds envisages sharing
The formation of the Cl2 molecule can be of more than one electron pair between two
understood in terms of the sharing of a pair atoms. if two atoms share two pairs of
Moose
of electrons between the two chlorine atoms, electrons, the covalent bond between them
each chlorine atom contributing one electron is called a double bond. For example, in the
say both
to the shared pair. In the process carbon dioxide molecule, we have two double
bonds between the carbon and oxygen atoms.
Similarly in ethene molecule the two carbon
atoms are joined by a double bond.
Hi
iq
or Cl – Cl
pEE
Covalent bond between two Cl atoms Double bonds in CO2 molecule
number of valence electrons. For example,

for the CO32– ion, the two negative charges
indicate that there are two additional
electrons than those provided by the
neutral atoms. For NH +4 ion, one positive
charge indicates the loss of one electron
toes see
from the group of neutral atoms.
C2H4 molecule
• Knowing the chemical symbols of the
when combining atoms share three
of
electron pairs as in the case of two nitrogen
combining atoms and having knowledge
of the skeletal structure of the compound
atoms in the n2 molecule and the two (known or guessed intelligently), it is easy
carbon atoms in the ethyne molecule, a to distribute the total number of electrons
2AM
triple bond is formed. as bonding shared pairs between the
atoms in proportion to the total bonds.
any • In general the least electronegative atom
to
occupies the central position in the
molecule/ion. For example in the NF3 and
CO32–, nitrogen and carbon are the central
N2 molecule
to one
atoms whereas fluorine and oxygen
occupy the terminal positions.
Dei • After accounting for the shared pairs of
electrons for single bonds, the remaining
C2H2 molecule electron pairs are either utilized for
Ieee
multiple bonding or remain as the lone
pairs. The basic requirement being
Ieee
4.1.3 Lewis Representation of Simple
Molecules (the Lewis Structures) that each bonded atom gets an octet of
electrons.
the Lewis dot structures provide a picture
of bonding in molecules and ions in terms of Lewis representations of a few molecules/
the shared pairs of electrons and the octet ions are given in Table 4.1.
tee
rule. While such a picture may not explain
the bonding and behaviour of a molecule table 4.1 the Lewis Representation of
completely, it does help in understanding the Some Molecules
formation and properties of a molecule to a
large extent. Writing of Lewis dot structures of
molecules is, therefore, very useful. The Lewis
dot structures can be written by adopting the
BEEBE
following steps:
• The total number of electrons required
for writing the structures are obtained
by adding the valence electrons of the
combining atoms. For example, in the CH4
t.ge
is
molecule there are eight valence electrons
available for bonding (4 from carbon and
4 from the four hydrogen atoms).
• For anions, each negative charge would
mean addition of one electron. For cations,
each positive charge would result in * Each H atom attains the configuration of helium
subtraction of one electron from the total (a duplet of electrons)
104 chemistry
problem 4.1 each of the oxygen atoms completing the

octets on oxygen atoms. This, however,
Write the Lewis dot structure of CO
does not complete the octet on nitrogen
molecule.
if the remaining two electrons constitute
Solution lone pair on it.
Step 1. Count the total number of valence
electrons of carbon and oxygen atoms.
The outer (valence) shell configurations
of carbon and oxygen atoms are: 2s2 2p2 Hence we have to resort to multiple
and 2s2 2p4, respectively. The valence bonding between nitrogen and one of
electrons available are 4 + 6 =10. the oxygen atoms (in this case a double
bond). This leads to the following Lewis
Step 2. The skeletal structure of CO is
dot structures.
written as: C O
trap
Step 3. Draw a single bond (one shared
electron pair) between C and O and
complete the octet on O, the remaining
two electrons are the lone pair on C.
or
Ataman
This does not complete the octet on
carbon and hence we have to resort to
multiple bonding (in this case a triple 4.1.4 Formal Charge
bond) between C and O atoms. This
satisfies the octet rule condition for both Lewis dot structures, in general, do not
atoms. represent the actual shapes of the molecules.
In case of polyatomic ions, the net charge is
possessed by the ion as a whole and not by
a particular atom. It is, however, feasible to
assign a formal charge on each atom. The
formal charge of an atom in a polyatomic
molecule or ion may be defined as the
problem 4.2
difference between the number of valence
Write the Lewis structure of the nitrite electrons of that atom in an isolated or free
ion, NO2– . state and the number of electrons assigned
to that atom in the Lewis structure. It is
Solution expressed as :
Step 1. Count the total number of
valence electrons of the nitrogen atom, Formal charge (F.C.)
the oxygen atoms and the additional one on an atom in a Lewis =
negative charge (equal to one electron). structure
MEEEE
N(2s2 2p3), O (2s2 2p4)
5 + (2 × 6) +1 = 18 electrons total number of valence total number of non
electrons in the free — bonding (lone pair)
I
Step 2. The skeletal structure of NO2– is atom electrons
written as : O N O total number of
Step 3. Draw a single bond (one shared — (1/2) bonding (shared)
electrons
electron pair) between the nitrogen and
The counting is based on the assumption 4.1.5 Limitations of the Octet Rule
that the atom in the molecule owns one The octet rule, though useful, is not universal.
electron of each shared pair and both the It is quite useful for understanding the
electrons of a lone pair. structures of most of the organic compounds
and it applies mainly to the second period
Let us consider the ozone molecule (O3).
The Lewis structure of O3 may be drawn as:
tee
elements of the periodic table. There are three
types of exceptions to the octet rule.
The incomplete octet of the central atom
In some compounds, the number of electrons
surrounding the central atom is less than
tee
eight. This is especially the case with elements
TEE
having less than four valence electrons.
The atoms have been numbered as 1, 2 gates
Examples are LiCl, BeH2 andtoooooBCl3.
and 3. The formal charge on:
• The central O atom marked 1
1 Li, Be and B have 1, 2 and 3 valence electrons
•
toga
=6–2–
2
(6) = +1
The end O atom marked 2

only. Some other such compounds are AlCl3
and BF3.
Odd-electron molecules
1
any
=6–4– (4) = 0 In molecules with an odd number of electrons
2
like nitric oxide, NO and nitrogen dioxide,
• The end O atom marked 3 NO2, the octet rule is not satisfied for all the
1
a
atoms
BABY
=6–6– (2) = –1
2
00
too
Hence, we represent O3 along with the
formal charges as follows: The expanded octet
Elements in and beyond the third period of
toys
the periodic table have, apart from 3s and 3p
o
orbitals, 3d orbitals also available for bonding.
a
In a number of compounds of these elements
there are more than eight valence electrons
We must understand that formal charges go
around the central atom. This is termed as
do not indicate real charge separation within
BE
the molecule. Indicating the charges on the tooo
the expanded octet. Obviously the octet rule
does not apply in such cases.
atoms in the Lewis structure only helps in
Some of the examples of such compounds
keeping track of the valence electrons in
tea
the molecule. Formal charges help in the
are: PF 5 , SF 6 , H 2 SO 4 and a number of
coordination compounds.
selection of the lowest energy structure from
Beer
a number of possible Lewis structures for a
oootf10
given species. Generally the lowest energy
structure is the one with the smallest
formal charges on the atoms. the formal
charge is a factor based on a pure covalent
view of bonding in which electron pairs
are shared equally by neighbouring atoms. i go Is
106 chemistry
Interestingly, sulphur also forms many affinity, is the negative of the energy change
compounds in which the octet rule is obeyed. accompanying electron gain.
In sulphur dichloride, the S atom has an octet Obviously ionic bonds will be formed
of electrons around it. more easily between elements with
comparatively low ionization enthalpies
t
offset
Other drawbacks of the octet theory
and elements with comparatively high
negative value of electron gain enthalpy.
Most ionic compounds have cations
as
• It is clear that octet rule is based upon derived from metallic elements and anions
the chemical inertness of noble gases. from non-metallic elements. The ammonium
However, some noble gases (for example ion, NH 4+ (made up of two non-metallic
xenon and krypton) also combine with
Bagger sage
ONE
oxygen and fluorine to form a number of
elements) is an exception. It forms the cation
of a number of ionic compounds.
Batastasy
compounds like XeF2, KrF2, XeOF2 etc.
• This theory does not account for the shape
Ionic compounds in the crystalline
state consist of orderly three-dimensional
of molecules. EAE arrangements of cations and anions held
• It does not explain the relative stability of together by coulombic interaction energies.
the molecules being totally silent about These compounds crystallise in different
the energy of a molecule. crystal structures determined by the size of
the ions, their packing arrangements and
4.2 iOniC OR ELECtROvALEnt BOnD other factors. The crystal structure of sodium
From the Kössel and Lewis treatment of the chloride, NaCl (rock salt), for example is
formation of an ionic bond, it follows that the shown below.
formation of ionic compounds would primarily
depend upon:
• The ease of formation of the positive and
negative ions from the respective neutral
atoms;
• The arrangement of the positive and
negative ions in the solid, that is, the
lattice of the crystalline compound.
Dost
The formation of a positive ion involves
ionization, i.e., removal of electron(s) from
Is
the neutral atom and that of the negative
neutral atom. Toooo

ion involves the addition of electron(s) to the Rock salt structure
In ionic solids, the sum of the electron gain
M(g) → M+(g) + e– ;
god Ionization enthalpy
enthalpy and the ionization enthalpy may be
positive but still the crystal structure gets
X(g) + e– → X – (g) ;
Boaz
Electron gain enthalpy
03
stabilized due to the energy released in the
03
formation of the crystal lattice. For example:
the ionization enthalpy for Na+(g) formation
M (g) + X (g) → MX(s)
+ –
The electron gain enthalpy, ∆eg H, is the EBay

from Na(g) is 495.8 kJ mol–1 ; while the electron
gain enthalpy for the change Cl(g) + e–→
enthalpy change (Unit 3), when a gas phase Cl– (g) is, – 348.7 kJ mol–1 only. The sum of the
atom in its ground state gains an electron.
38s
The electron gain process may be exothermic
y
Bto
two, 147.1 kJ mol-1 is more than compensated
see
for by the enthalpy of lattice formation of
Ltg
or endothermic. The ionization, on the other
hand, is always endothermic. Electron
NaCl(s) (–788 kJ mol ). Therefore, the energy
Buzz
–1
released in the processes is more than the
energy absorbed. thus a qualitative measure

of the stability of an ionic compound
is provided by its OEoaseaaa.ee
enthalpy
FN of lattice
formation and not simply by achieving
octet of electrons around the ionic species
copy
in gaseous state.
Since lattice enthalpy plays a key role
in the formation of ionic compounds, it is
important that we learn more about it.
4.2.1 Lattice Enthalpy
the Lattice Enthalpy of an ionic solid
is defined as the energy required to
completely separate one mole of a solid
toooo
ionic compound into gaseous constituent
ions. For example, the lattice enthalpy of
NaCl is 788 kJ mol–1. This means that 788 Fig. 4.1 The bond length in a covalent
th
kJ of energy is required to separate one mole molecule AB.
of solid NaCl into one mole of Na+ (g) and one
m ease
R = rA + rB (R is the bond length and rA and rB are
se
ga
mole of Cl– (g) to an infinite distance. the covalent radii of atoms A and B
respectively)
This process involves both the attractive
forces between ions of opposite charges
in the same molecule. the van der waals
and the repulsive forces between ions of radius represents the overall size of the
like charge. The solid crystal being three- Ite
atom which includes its valence shell in a
dimensional; it is not possible to calculate nonbonded situation. Further, the van der
lattice enthalpy directly from the interaction Waals radius is half of the distance between
of forces of attraction and repulsion only. two similar atoms in separate molecules in
Factors associated with the crystal geometry a solid. Covalent and van der Waals radii of
have to be included. chlorine are depicted in Fig. 4.2.
4.3 BOnD pARAMEtERS
rc = 99 pm 19
4.3.1 Bond Length 8
pm
_fftB_
Bond length is defined as the equilibrium
distance between the nuclei of two bonded
_t in a molecule. Bond lengths
atoms
tooare
peggy
measured by spectroscopic, X-ray diffraction
and electron-diffraction techniques about
which you will learn in higher classes. Each
atom of the bonded pair contributes to the
r vd
w
=
bond length (Fig. 4.1). In the case of a covalent

18
0
bond, the contribution from each atom is

pm
called the covalent radius of that atom.

pm
0
36
the covalent radius is measured

approximately as the radius of an atom’s
Fig. 4.2 Covalent and van der Waals radii in
core which is in contact with the core of an a chlorine molecule. The inner circles
adjacent atom in a bonded situation. The correspond to the size of the chlorine
covalent radius isWEE
half of the distance between atom (rvdw and rc are van der Waals and
Taj
two similar atoms joined by a covalent bond covalent radii respectively).
108 chemistry
Some typical average bond lengths for table 4.2 Average Bond Lengths for Some
single, double and triple bonds are shown in Single, Double and triple Bonds
Table 4.2. Bond lengths for some common
Covalent Bond
molecules are given in Table 4.3. Bond type
Length (pm)
The covalent radii of some common
O–H 96
elements are listed in Table 4.4.
C–H 107
4.3.2 Bond Angle N–O 136
C–O 143
It is defined as the angle between the orbitals
C–N 143
containing bonding electron pairs around the
Sgt
central atom in a molecule/complex ion. Bond
C–C
C=O
154
121
angle is expressed in degree which can be
pops
experimentally determined by spectroscopic
N=O
C=C
122
133
methods. It gives some idea regarding the C=N 138
distribution of orbitals around the central C≡N 116
atom in a molecule/complex ion and hence it C≡C 120
helps us in determining its shape. For
example H–O–H bond angle in water Thecan be table 4.3 Bond Lengths in Some Common
Molecules
represented as under :
Molecule Bond Length (pm)
H2 (H – H) 74
eggs F2 (F – F) 144
4.3.3 Bond Enthalpy Cl2 (Cl – Cl) 199
It is defined as the amount of energy required Br2 (Br – Br) 228
t e
to break one mole of bonds of a particular
type between two atoms in a gaseous state.
S
g I2 (I – I)
N2 (N ≡ N)
267
109
LE
The unit of bond enthalpy is kJ mol–1. For O2 (O = O) 121
ES
example, the H – H bond enthalpy in hydrogen HF (H – F) 92
molecule is 435.8 kJ mol .–1 HCl (H – Cl) 127
HBr (H – Br) 141
H2(g) → H(g) + H(g); ∆aH = 435.8 kJ mol–1
to HI (H – I) 160
Similarly the bond enthalpy for molecules
containing multiple bonds, for example O2 and table 4.4 Covalent Radii, *rcov/(pm)
N2 will be as under :
O2 (O = O) (g) → O(g) + O(g);
∆aH = 498 kJ mol–1
Ess
N2 (N ≡ N) (g) → N(g) + N(g);
a
∆aH = 946.0 kJ mol–1
It is important that larger the bond
dissociation enthalpy, stronger will be the
bond in the molecule. ForIsa heteronuclear
diatomic molecules like HCl, we have
HCl (g) → H(g) + Cl (g); ∆aH = 431.0 kJ mol–1
In case of polyatomic molecules, the
measurement of bond strength is more
complicated. For example in case of H 2O * The values cited are for single bonds, except where
molecule, the enthalpy needed to break the otherwise indicated in parenthesis. (See also Unit 3 for
two O – H bonds is not the same. periodic trends).
to
H2O(g) → H(g) + OH(g); ∆aH1 = 502 kJ mol–1
ai at
OH(g) → H(g) + O(g); ∆aH2 = 427 kJ mol–1
The difference in the ∆aH value shows
that the second O – H bond undergoes
some change because of changed chemical
environment. This is the reason for some
difference in energy of the same O – H bond
in different molecules like C2H5OH (ethanol)
and water. Therefore in polyatomic molecules
the term mean e or average bond enthalpy
type
oooo
is used. It is obtained by dividing total bond
dissociation enthalpy by the number of bonds
broken as explained below in case of water
molecule,
502 + 427 Fig. 4.3 Resonance in the O3 molecule
Average bond enthalpy =
2
(structures I and II represent the two canonical
= 464.5 kJ mol–1
as forms while the structure III is the resonance hybrid)
4.3.4 Bond Order
in the Lewis description of covalent bond, In both structures we have a O–O single
the Bond Order is given by the number bond and a O=O double bond. The normal
of bonds between the two atoms in a
St
g of
molecule. The bond order, for example in
O–O and O=O bond lengths are 148 pm
and 121 pm respectively. Experimentally
orgs
H2 (with a single shared electron pair), in O2
(with two shared electron pairs) and in N2
(with three shared electron pairs) is 1,2,3
to
sy
zetas
determined oxygen-oxygen bond lengths in
the O3 molecule are same (128 pm). Thus the
oxygen-oxygen bonds in the O3 molecule are
respectively. Similarly in CO (three
see shared intermediate between a double and a single
electron pairs between C and O) the bond _aaa too
bond. Obviously, this cannot be represented too
order is 3. For N2, bond order is 3 and its by either of the two Lewis structures shown
is 946 kJ mol–1; being one of the highest
for a diatomic molecule.
too above.
The concept of resonance was introduced
isoelectronic molecules and ions have to deal with the type of difficulty experienced
identical bond orders; for example, F2 and in the depiction of accurate structures of
O22– have bond order 1. n2, CO and nO+ have molecules like O3. According to the concept
bond order 3. of resonance, whenever a single Lewis
A general correlation useful for structure cannot describe a molecule East
understanding the stablities of molecules accurately, a number of structures with
similar energy, positions of nuclei, bonding
is that: with increase in bond order, oooo
33oz
goatees
bond enthalpy increases and bond length and non-bonding pairs of electrons are
taken as the canonical structures of the
decreases.
yegg
hybrid which describes the molecule
4.3.5 Resonance Structures accurately. Thus for O3, the two structures
It is often observed that a single Lewis structure shown above constitute the canonical
is inadequate for the representation of a structures or resonance structures and
molecule in conformity with its experimentally their hybrid i.e., the III structure represents
determined parameters. For example, the the structure of O3 more accurately. This is
ozone, O3 molecule can be equally represented also called resonance hybrid. Resonance is
by the structures I and II shown below: represented by a double ft headed arrow.
110 chemistry
Some of the other examples of resonance

structures are provided by the carbonate ion
Boot
and the carbon dioxide molecule.
problem 4.3 Fig. 4.5 Resonance in CO 2 molecule, I, II

and III represent the three canonical
Explain the structure of CO32– ion in forms.
terms of resonance.
Solution in general, it may be stated that
The single Lewis structure based on • Resonance stabilizes the molecule as the
the presence of two single bonds and energy of the resonance hybrid is less
one double bond between carbon than the energy of any single cannonical
and oxygen atoms is inadequate to structure; and,
represent the molecule accurately as it
represents unequal bonds. According
• Resonance averages the bond
characteristics as a whole.
to the experimentalKo findings, all carbon
to oxygen bonds in CO32– are equivalent. Thus the energy of the O 3 resonance
Therefore the carbonate ion is best hybrid is lower than either of the two
described as a resonance hybrid of the cannonical froms I and II (Fig. 4.3).
canonical forms I, II, and III shown below.
Many misconceptions are associated
with resonance and the same need to be
dispelled. You should remember that :
• The cannonical forms have no real
Boogie
existence.
tooo
• The molecule does not exist for a certain
fraction of time in one cannonical form
and for other fractions of time in other
Fig. 4.4 Resonance in CO32–, I, II and III cannonical forms.
represent the three canonical • There is no such equilibrium between
forms. the cannonical forms as we have
problem 4.4 between tautomeric forms (keto and
o
Explain the structure of CO2 molecule. enol) in tautomerism.
• The molecule as such has a single
Solution structure which is the resonance
The experimentally determined carbon hybrid of the cannonical forms and
to oxygen bond length in CO 2 is which cannot as such be depicted by
00g
115 pm. The lengths of a normal a single Lewis structure.
carbon to oxygen double bond (C=O)
E MBpgg.ae
and carbon to oxygen triple bond (C≡O) 4.3.6 polarity of Bonds
are 121 pm and 110 pm respectively.
The carbon-oxygen bond lengths in The existence of a hundred percent ionic or
CO2 (115 pm) lie between the values covalent bond represents an ideal situation.
for C=O and C≡O. Obviously, a single In reality no bond or a compound is either
Lewis structure cannot depict this completely covalent or ionic. Even in case of
position and it becomes necessary to covalent bond between two hydrogen atoms,
write more than one Lewis structures there is some ionic character.
and to consider that the structure of
CO2 is best described as a hybrid of When covalent bond is formed between
the canonical or resonance forms I, II two similar atoms, for example in H2, O2,
and III. Cl2, N2 or F2, the shared pair of electrons is
equally attracted by the two atoms. As a result
electron pair is situated exactly between the In case of polyatomic molecules the dipole
two identical nuclei. The bond so formed is moment not only depend upon the individual
called nonpolar covalent bond. Contrary to dipole moments of bonds known as bond
to
this in case of a heteronuclear molecule like
too
dipoles but also on the spatial arrangement
gets
HF, the shared electron pair between the two of various bonds in the molecule. In such
atoms gets displaced more towards fluorine case, the dipole moment of a molecule is the
since the electronegativity of fluorine (Unit 3) vector sum of the dipole moments of various
NoggMt these
_I_
is far greater than that of hydrogen. The bonds. For example in H2O molecule, which
resultant covalent bond is a polar covalent
bond. mega these
has a bent structure, the two O–H bonds are
oriented at an angle of 104.50. Net dipole
fat
As a result of polarisation, the molecule moment of 6.17 × 10–30 C m (1D = 3.33564
possesses the dipole moment (depicted × 10–30 C m) is the resultant of the dipole
below) which can be defined as the product of moments of two O–H bonds.
the magnitude of the charge and the distance
Toto
between the centres of positive and negative
to
tog
do
charge. It is usually designated by a Greek
letter ‘µ’. Mathematically, it is expressed as
follows :
Dipole moment (µ) = charge (Q) × distance of
Booboos Date
separation (r)
Tests
Dipole moment is usually expressed in Net Dipole moment, µ = 1.85 D
Debye units (D). The conversion factor is = 1.85 × 3.33564 × 10–30 C m = 6.17 ×10–30 C m
Gas
1 D = 3.33564 × 10–30 C m Taste
The dipole moment in case of BeF2 is zero.
where C is coulomb and m is meter.
This is because the two equal bond dipoles
Further dipole moment is a vector quantity point in opposite directions and cancel the
and by convention it is depicted by a small effect of each other.
arrow with tail on the negative centre and
to
head pointing towards the positive centre.
But in chemistry presence of dipole moment asset
is represented by the crossed arrow ( go )
put on Lewis structure of the molecule. The In tetra-atomic molecule, for example in
cross is on positive end and arrow head is on BF3, the dipole moment is zero although the
negative end. For example the dipole moment to
of HF may be represented as : Cee
B – F bonds are oriented at an angle of 120o
to one another, the three bond moments give
Foon
H F
a net sum of zero as the resultant of any two
This arrow symbolises the direction of the Bao Bothe
is equal and opposite to the third.
shift of electron density in the molecule. Note
that the direction of crossed arrow is opposite
to the conventional direction of dipole moment
vector.
Peter Debye, the Dutch chemist

received Nobel prize in 1936 for
Let us study an interesting case of NH3
his work on X-ray diffraction and
dipole moments. The magnitude
and NF3 molecule. Both the molecules have
of the dipole moment is given in pyramidal shape with a lone pair of electrons
on nitrogen atom. Although fluorine is more
Debye units in order to honour him.
thEfagogy
electronegative than nitrogen, the resultant
112 chemistry
dipole moment of NH3 (4.90 × 10–30 C m) is The smaller the size of the cation and the
greater than that of NF3 (0.8 × 10–30 C m). This
•
for
larger the size of the anion, the greater
one
Beta
is because, in case of NH3 the orbital dipole the covalent character of an ionic bond.
due to lone pair is in the same direction as
the resultant dipole moment on of the N – H • The greater the charge on the cation, the
greater the covalent character of the ionic
bonds, whereas in NF3 the orbital dipole is in bond. Least
the direction opposite to the resultant dipole
tape
moment of the three N–F bonds. The orbital
• For cations of the same size and charge,
3oz configuration
the one, with electronic
dipole because of lone pair decreases the effect
(n-1)dnnso, typical of transition metals, is
of the resultant N – F bond moments, which
more polarising than the one with a noble
results in the low dipole moment of NF3 as
represented below :
Boss
gas configuration, ns2 np6, typical of alkali
and alkaline earth metal cations.
The cation polarises the anion, pulling
to
the electronic charge toward itself and
signora's
thereby increasing the electronic charge
between the two. This is precisely what
happens in a covalent bond, i.e., buildup
of electron charge density between the
nuclei. The polarising power of the cation,
Matheos
the polarisability of the anion and the
extent of distortion (polarisation) of anion
are the factors, which determine the per
Dipole moments of some molecules are cent covalent character of the ionic bond.
shown in Table 4.5. MEEEEE toss
Just as all the covalent bonds have 4.4 tHE vALEnCE SHELL ELECtROn
some partial ionic character, the ionic pAiR REpULSiOn (vSEpR) tHEORy
bonds also have partial covalent character. As already explained, Lewis concept is unable
tf
the partial covalent character of ionic to explain the shapes of molecules. This
bonds was discussed by Fajans in terms of egg theory provides a simple procedure to predict
the following rules: the shapes of covalent molecules. Sidgwick
top toy
table 4.5 Dipole Moments of Selected Molecules
Dipole
type of Molecule Example Geometry
Moment, µ(D)
Molecule (AB) HF 1.78 linear
ay
HCl 1.07 linear
HBr 0.79 linear
Hl 0.38 linear
H2 0 linear
Molecule (AB2) H2O 1.85 bent
at
H2S 0.95 bent
CO2 0 linear
Molecule (AB3) NH3 1.47 trigonal-pyramidal
yea
NF3 0.23 trigonal-pyramidal
BF3 0 trigonal-planar
Molecule (AB4) CH4 0 tetrahedral
CHCl3
CCl4
1.04
0 Ng
tetrahedral
tetrahedral
and Powell in 1940, proposed a simple theory result in deviations from idealised shapes and
based on the repulsive interactions of the alterations in bond angles in molecules.
electron pairs in the valence shell of the For the prediction of geometrical shapes
atoms. It was further developed and redefined of molecules with the help of VSEPR theory,
by Nyholm and Gillespie (1957). it is convenient to divide molecules into
the main postulates of vSEpR theory are two categories as (i) molecules in which
as follows: the central atom has no lone pair and
Baggage
(ii) molecules in which the central atom
• The shape of a molecule depends upon
has one or more lone T pairs.
the number of valence shell electron pairs
et test
(bonded or nonbonded) around the central Table 4.6 (page114) shows the
atom.
izz arrangement of electron pairs about a
• Pairs of electrons in the valence shell repel central atom A (without any lone pairs) and
E
one another since their electron clouds are geometries of some molecules/ions of the type
negatively charged. AB. Table 4.7 (page 115) shows shapes of some
•
Met
These pairs of electrons tend to occupy
simple molecules and ions in which the central
atom has one or more lone pairs. Table 4.8
such positions in space that minimise
gtf
repulsion and thus maximise distance
between them.
(page 116) explains the reasons for the
distortions in the geometry of the molecule.
• The valence shell is taken as a sphere As depicted in Table 4.6, in the

with the electron pairs localising on the compounds of AB2, AB3, AB4, AB5 and AB6,
spherical surface at maximum distance the arrangement of electron pairs and the
tEEE
from one another. B atoms around the central atom A are :
linear, trigonal planar, tetrahedral,
N
• A multiple bond is treated as if it is a single
electron pair and the two or three electron
Not
pairs of a multiple bond are treated as a
NRosa
trigonal-bipyramidal and octahedral,
respectively. Such arrangement can be seen
in the molecules like BF3 (AB3), CH4 (AB4) and
single super pair.
•
More
Where two or more resonance structures
PCl5 (AB5) as depicted below by their ball and
fat
can represent a molecule, the VSEPR
stick models.
model is applicable to any such structure.

the repulsive interaction of electron pairs
Dooooooooooooigg
decrease in the order:
Lone pair (lp) – Lone pair (lp) > Lone pair
(lp) – Bond pair (bp) > Bond pair (bp) –
Bond pair (bp) Fig. 4.6 The shapes of molecules in which
central atom has no lone pair
Nyholm and Gillespie (1957) refined the
VSEPR model by explaining the important The VSEPR Theory is able to predict
F DIESEL
difference between the lone pairs and bonding
pairs of electrons. While the lone pairs are
geometry of a large number of molecules,
especially the compounds of p-block elements
localised on the central atom, each bonded accurately. It is also quite successful in
pair is shared between two atoms. As a result, determining the geometry quite-accurately
the lone pair electrons in a molecule occupy even when the energy difference between
more space as compared to the bonding pairs possible structures is very small. The
E_
of electrons. This results in greater repulsion theoretical basis of the VSEPR theory regarding
EÉEE
between lone pairs of electrons as compared the effects of electron pair repulsions on
to the lone pair - bond pair and bond pair - molecular shapes is not clear and continues
bond pair repulsions. These repulsion effects to be a subject of doubt and discussion.
114 chemistry
table 4.6 Geometry of Molecules in which the Central Atom has no Lone pair of Electrons
to
Bty
Mtbe
table 4.7 Shape (geometry) of Some Simple Molecules/ions with Central ions having
One or More Lone pairs of Electrons(E).
Egger
Eg
ayyy
t go
say
Eto
116 chemistry
table 4.8 Shapes of Molecules containing Bond pair and Lone pair
Molecule no. of no. of Arrangement Shape Reason for the
type bonding lone of electrons shape acquired
pairs pairs
AB2E 4 1 Bent Theoretically the shape
toooo
should have been triangular
planar but actually it is found
to be bent or v-shaped. The
reason being the lone pair-
bond pair repulsion is much
more as compared to the bond
pair-bond pair repulsion. So
the angle is reduced to 119.5°
from 120°.
AB3E 3 1 Trigonal Had there been a bp in place

of lp the shape would have
pyramidal
been tetrahedral but one
lone pair is present and due
to the repulsion between
Bagg lp-bp (which is more than
bp-bp repulsion) the angle
between bond pairs is
reduced to 107° from 109.5°.
Bent The shape should have been

AB2E2 2 2 tetrahedral if there were all bp
but two lp are present so the
shape is distorted tetrahedral
Peggy
or angular. The reason is
lp-lp repulsion is more than
lp-bp repulsion which is more
than bp-bp repulsion. Thus,
the angle is reduced to 104.5°
from 109.5°.
AB4E 4 1 See- In (a) the lp is present at axial

saw position so there are three
Abkhaz
lp—bp repulsions at 90°.
In(b) the lp is in an equatorial
position, and there are two
lp—bp repulsions. Hence,
arrangement (b) is more
stable. The shape shown in
(b) is described as a distorted
tetrahedron, a folded square
(More stable) or a see-saw.
Molecule no. of no. of Arrangement Shape Reason for the

type bonding lone of electrons shape acquired
pairs pairs
AB3E2 3 2 T-shape In (a) the lp are at

equatorial position
so there are less lp-
bp repulsions as
compared to others
in which the lp are
at axial positions. So
structure (a) is most
stable. (T-shaped).
tape
4.5 vALEnCE BOnD tHEORy of the valence bond theory is based on the
As we know that Lewis approach helps in knowledge of atomic orbitals, electronic
writing the structure of molecules but it configurations of elements (Units 2), the
fails to explain the formation of chemical overlap criteria of atomic orbitals, the
bond. It also does not give any reason for the hybridization of atomic orbitals and the
principles of variation and superposition. A
difference in bond dissociation enthalpies and
rigorous treatment of the VB theory in terms
bond lengths in molecules like H2 (435.8 kJ
as Et
mol-1, 74 pm) and F2 (155 kJ mol-1, 144 pm),
although in both the cases a single covalent
of these aspects is beyond the scope of this
book. Therefore, for the sake of convenience,
valence bond theory has been discussed in
bond is formed by the sharing of an electron
terms of qualitative and non-mathematical
toy
pair between the respective atoms. It also treatment only. To start with, let us consider
gives no idea about the shapes of polyatomic the formation of hydrogen molecule which is
molecules. the simplest of all molecules.
Similarly the VSEPR theory gives the Consider two hydrogen atoms A and B
geometry of simple molecules but theoretically, approaching each other having nuclei NA
it does not explain them and also it has limited and NB and electrons present in them are
applications. To overcome these limitations represented by eA and eB. When the two atoms
the two important theories based on quantum are at large distance from each other, there
mechanical principles are introduced. These is no interaction between them. As these two
are valence bond (VB) theory and molecular atoms approach each other, new attractive
orbital (MO) theory. and repulsive forces begin to operate.
valence bond theory was introduced Attractive forces arise between:
by Heitler and London (1927) and developed (i) nucleus of one atom and its own electron
further by Pauling and others. A discussion
to
that is NA – eA and NB– eB.
eat
118 chemistry
(ii) nucleus of one atom and electron of together to form a stable molecule having the
soooooo
other atom i.e., NA– eB, NB– eA. bond length of 74 pm.
t oooo
Similarly repulsive forces arise between Since the energy gets released when the
(i) electrons of two atoms like eA – eB, bond is formed between two hydrogen atoms,
the hydrogen molecule is more stable than
(ii) nuclei of two atoms NA – NB. t The energy
that of isolated hydrogen atoms.
Do
Attractive forces tend to bring the two
atoms close to each other whereas repulsive
Itp
so released is called as bond enthalpy, which
Toyota
is corresponding to minimum in the curve
forces tend to push them apart (Fig. 4.7). depicted in Fig. 4.8. Conversely, 435.8 kJ of
goes
energy is required to dissociate one mole of
H2 molecule.
H2(g) + 435.8 kJ mol–1 → H(g) + H(g)
Ha
Fig. 4.8 The potential energy curve for the

formation of H2 molecule as a function
of internuclear distance of the H atoms.
notes
The minimum in the curve corresponds
to the most stable state of H2.
4.5.1 Orbital Overlap Concept

In the formation of hydrogen molecule,
there is a minimum energy state when two
hydrogen atoms are so near that their atomic
Fig. 4.7 Forces of attraction and repulsion
orbitals undergo partial interpenetration. This
during the formation of H2 molecule partial merging of atomic orbitals is called
overlapping of atomic orbitals which results in
Athyn
Experimentally it has been found that
the pairing of electrons. The extent of overlap
the magnitude of new attractive force is
Dotforces. As a decides the strength of a covalent bond. In to
more than the new repulsive
D
result, two atoms approach each other and general, greater the overlap the stronger is the
38 eggs
potential energy decreases. Ultimately a stage bond formed between two atoms. Therefore,
Mat
is reached where the net force of attraction according to orbital overlap concept, the
balances the force of repulsion and system formation of a covalent bond between two
got
acquires minimum energy. At this stage
two hydrogen atoms are said to be bonded
atoms results by pairing of electrons present
to
in the valence shell having opposite spins.
too
4.5.2 Directional properties of Bonds

As we have already seen, the covalent bond
is formed by overlapping of atomic orbitals.
The molecule of hydrogen is formed due to the
BE
overlap of 1s-orbitals of two H atoms.
In case of polyatomic molecules like CH4,
NH3 and H2O, the geometry of the molecules
is also important in addition to the bond
formation. For example why is it so that CH4
Effete
molecule has tetrahedral shape and HCH
bond angles are 109.5°? Why is the shape of
Boty
NH3 molecule pyramidal ?
The valence bond theory explains the
shape, the formation and directional properties
st
of bonds in polyatomic molecules like CH4,
NH3 and H2O, etc. in terms of overlap and
hybridisation of atomic orbitals.
4.5.3 Overlapping of Atomic Orbitals
When orbitals of two atoms come close to form
bond, their overlap may be positive, negative
of
as (phase) and
Be bae
or zero depending upon the sign
direction of orientation of amplitude of orbital
magpie
wave function in space (Fig. 4.9). Positive and
negative sign on boundary surface diagrams
in the Fig. 4.9 show the sign (phase) of orbital
wave function and are not related to charge.
soft go
Orbitals forming bond should have same sign
(phase) and orientation in space. This is called
Fig.4.9 Positive, negative and zero overlaps of
s and p atomic orbitals
positive overlap. Various overlaps of s and p hydrogen. The four atomic orbitals of carbon,
soo
orbitals are depicted in Fig. 4.9. each with an unpaired electron can overlap
The criterion of overlap, as the main factor Ba

with the 1s orbitals of the four H atoms which
are also singly occupied. This will result in the
for the formation of covalent bonds applies formation of four C-H bonds. It will, however,
uniformly to the homonuclear/heteronuclear Tas
be observed that while the three p orbitals of
diatomic molecules and polyatomic molecules.
We know that the shapes of CH4, NH3, and Ba
carbon are at 90° to one another, the HCH
angle for these will also be 90°. That is three
H2O molecules are tetrahedral, pyramidal
Fatso
and bent respectively. It would be therefore
C-H bonds will be oriented at 90° to one
another. The 2s orbital of carbon and the 1s
interesting to use VB theory to find out if these go
orbital of H are spherically symmetrical and
to
geometrical shapes can be explained in terms they can overlap in any direction. Therefore
of the orbital overlaps. the direction of the fourth C-H bond cannot
Let us first consider the CH4 (methane) be ascertained. This description does not fit
molecule. The electronic configuration of
carbon in its ground state is [He]2s2 2p2 which ask
in with the tetrahedral HCH angles of 109.5°.
to
Clearly, it follows that simple atomic orbital
in the excited state becomes [He] 2s1 2px1 2py1 overlap does not account for the directional
to
2pz1. The energy required for this excitation is characteristics of bonds in CH4. Using similar
compensated by the release of energy due to procedure and arguments, it can be seen that in
overlap between the orbitals of carbon and the the case of NH3 and H2O molecules, the HNH
120 chemistry
and HOH angles should be 90°. This is in above and below the plane of the
t x
disagreement with the actual bond angles of participating atoms.
as E
107° and 104.5° in the NH3 and H2O molecules
respectively.
E
Soggy
toffee
4.5.4 types of Overlapping and nature of
Covalent Bonds
The covalent bond may be classified into
two types depending upon the types of
overlapping:
(i) Sigma(σ) bond, and (ii) pi(π) bond
(i) Sigma(σ) bond : This type of covalent 4.5.5 Strength of Sigma and pi Bonds
bond is formed by the end to end (head-
Bthd
on) overlap of bonding orbitals along the
Basically the strength of a bond depends
as
internuclear axis. This is called as head
upon the extent of overlapping. In case of
see
to
on overlap or axial overlap. This can be
sigma bond, the overlapping of orbitals takes
tape assegai
formed by any one of the following types
place to a larger extent. Hence, it is stronger
ftp Rts
as compared to the pi bond where the extent
of combinations of atomic orbitals.
of overlapping occurs to a smaller extent.
• s-s overlapping : In this case, there is Ina
Further, it is important to note that in the
overlap of two half filled s-orbitals along
ted formation of multiple bonds between two
Age
the internuclear axis as shown below : atoms of a molecule, pi bond(s) is formed in
addition to a sigma bond.
Sg 6 g 4.6 HyBRiDiSAtiOn
In order to explain the characteristic
geometrical shapes of polyatomic molecules
• s-p overlapping: This type of overlap like CH4, NH3 and H2O etc., Pauling introduced
occurs between half filled s-orbitals of one the concept of hybridisation. According to him
Footage
atom and half filled p-orbitals of another
atom.
the atomic orbitals combine to form new set of
equivalent orbitals known as hybrid orbitals.
gatame
Unlike pure orbitals, the hybrid orbitals are
ME ooooo 030mg used in bond formation. The phenomenon is

known as hybridisation which can be defined
as the process of intermixing of the orbitals of
• p–p overlapping : This type of overlap slightly different energies so as to redistribute
takes place between half filled p-orbitals their energies, resulting in the formation of
of the two approaching atoms. __t new set of orbitals of equivalent energies and
shape. For example when one 2s and three
FREER DENEEN Noooot
T 2p-orbitals of carbon hybridise, there is the
formation of four new sp3 hybrid orbitals.
pages
Salient features of hybridisation: The main
(ii) pi( ) bond : In the formation of π bond features of hybridisation are as under :
the atomic orbitals overlap in such a
way that their axes remain parallel to 1. The number of hybrid orbitals is equal to
Site
the number of the atomic orbitals that get
each other and perpendicular to the
internuclear axis. The orbitals formed hybridised. too
on
due to sidewise overlapping consists 2. The hybridised orbitals are always
of two saucer type charged clouds equivalent in energy and shape.
tazz ooooo
3. The hybrid orbitals are more effective in vacant 2p orbital to account for its bivalency.
one
orbitals.
in
forming stable bonds than the pure atomic
ooze
One 2s and one 2p-orbital gets hybridised to
form two sp hybridised orbitals. These two
4. These hybrid orbitals are directed in sp hybrid orbitals are oriented in opposite
direction forming an angle of 180°. Each of
space in some preferred direction to have to
the sp hybridised orbital overlaps with the
toga
minimum repulsion between electron
pairs and thus a stable arrangement. 2p-orbital of chlorine axially and form two Be-
Therefore, the type of hybridisation Cl sigma bonds. This is shown in Fig. 4.10.
indicates the geometry of the molecules.
on
Bae
important conditions for hybridisation
(i) The orbitals present in the valence shell
of the atom are hybridised. g
Be
(ii) The orbitals undergoing hybridisation
should have almost equal energy.
t ooo ogEoggaaa
(iii) Promotion of electron is not essential
condition prior to hybridisation.
(iv) It is not necessary that only half filled
orbitals participate in hybridisation.
In some cases, even filled orbitals of
to
valence shell take part in hybridisation.
Fig.4.10 (a) Formation of sp hybrids from s and
4.6.1 types of Hybridisation p orbitals; (b) Formation of the linear
There are various types of hybridisation BeCl2 molecule
involving s, p and d orbitals. The different
(ii) sp2 hybridisation : In this hybridisation
types of hybridisation are as under:
there is involvement of one s and two
(i) sp hybridisation: This type of hybridisation toe Too
p-orbitals in order to form three equivalent
involves the mixing of one s and one p orbital
ten
resulting in the formation of two equivalent yard
sp 2 hybridised orbitals. For example, in
BCl3 molecule, the ground state electronic
sp hybrid orbitals. The suitable orbitals for
Bo
sp hybridisation are s and pz, if the hybrid
configuration of central boron atom is
B
orbitals are to lie along theasz-axis. Each sp 60866
1s22s22p1. In the excited state, one of the 2s
88
electrons is promoted to vacant 2p orbital as
Eo_
hybrid orbitals has 50% s-character and egg
50% p-character. Such a molecule in which
Bag
the central atom is sp-hybridised and linked
directly to two other central atoms possesses
linear geometry. This type of hybridisation is
Bag
also known as diagonal hybridisation.
oat
The two sp hybrids point in the opposite
direction along the z-axis with projecting
positive lobes and very small negative lobes,
was
Fae
which provides more effective overlapping
resulting in the formation of stronger bonds.
Example of molecule having sp
hybridisation
B e C l 2: T h e g r o u n d s t a t e e l e c t r o n i c
to
configuration of Be is 1s22s2. In the exited Fig.4.11 Formation of sp2 hybrids and the BCl3
go
state one of the 2s-electrons is promoted to molecule
122 chemistry
a result boron has three unpaired electrons. 2 1 1 1

ground state is 2S 2 p x 2 py 2 p z having three
These three orbitals (one 2s and two 2p)
t te g
Effie
unpaired electrons in the sp3 hybrid orbitals
hybridise to form three sp2 hybrid orbitals.
96K
The three hybrid orbitals so formed are
and a lone pair of electrons is present in the
Baggage
fourth one. These three hybrid orbitals overlap
oriented in a trigonal planar arrangement
with 1s orbitals of hydrogen atoms to form
and overlap with 2p orbitals of chlorine to
pop_S
three N–H sigma bonds. We know that the
form three B-Cl bonds. Therefore, in BCl3
force of repulsion between a lone pair and a
(Fig. 4.11), the geometry is trigonal planar
bond pair is more than the force of repulsion
with ClBCl bond angle of 120°.
Brygge
between two bond pairs of electrons. The
(iii) sp 3 hybridisation: This type of molecule thus gets distorted and the bond
hybridisation can be explained by taking the angle is reduced to 107° from 109.5°. The
example of CH4 molecule in which there is geometry of such a molecule will be pyramidal
mixing of one s-orbital and three p-orbitals
on Buzz
of the valence shell to form four sp3 hybrid
as shown in Fig. 4.13.
orbital of equivalent energies and shape. There
BE
is 25% s-character and 75% p-character in
each sp3 hybrid orbital. The four sp3 hybrid
too
orbitals so formed are directed towards the
four corners of the tetrahedron. The angle
am
between sp3 hybrid orbital is 109.5° as shown
in Fig. 4.12.
too o't
Fig.4.13 Formation of NH3 molecule
In case of H2O molecule, the four oxygen

orbitals (one 2s and three 2p) undergo sp3
hybridisation forming four sp3 hybrid orbitals
out of which two contain one electron each and
the other two contain a pair of electrons. These
σ four sp3 hybrid orbitals acquire a tetrahedral
geometry, with two corners occupied by
Foggia
σ σ
hydrogen atoms while the other two by the
lone pairs. The bond angle in this case is
σ reduced to 104.5° from 109.5° (Fig. 4.14)
and the molecule thus acquires a V-shape or
angular geometry.
Fig.4.12 Formation of sp 3 hybrids by the

combination of s, px , py and pz atomic
Baggage
orbitals of carbon and the formation of
CH4 molecule
The structure of NH3 and H2O molecules

can also be explained with the help of sp3
hybridisation. In NH3, the valence shell (outer)
electronic configuration of nitrogen in the Fig.4.14 Formation of H2O molecule
4.6.2 Other Examples of sp3, sp2 and sp used for making sp2–s sigma bond with two
Hybridisation t
hydrogen atoms. The unhybridised orbital (2px
sp3 Hybridisation in C2H6 molecule: In
ethane molecule both the carbon atoms t t
or 2py) of one carbon atom overlaps sidewise
with the similar orbital of the other carbon
assume sp3 hybrid state. One of the four atom to form weak π bond, which consists of
t
sp3 hybrid orbitals of carbon atom overlaps two equal electron clouds distributed above
axially with similar orbitals of other atom to 0
and below the plane of carbon and hydrogen
Bosse
form sp3-sp3 sigma bond while the other three atoms. 3333
hybrid orbitals of each carbon atom are used
Thus, in ethene molecule, the carbon-
d
in forming sp3–s sigma bonds with hydrogen
carbon bond consists of one sp2–sp2 sigma
at
atoms as discussed in section 4.6.1(iii).
Be
Therefore in ethane C–C bond length is 154
pm and each C–H bond length is 109 pm.
am
bond and one pi (π ) bond between p orbitals
which are not used in the hybridisation and
og
sp2 Hybridisation in C2H4: In the formation
are perpendicular to the plane of molecule; the
to
bond length 134 pm. The C–H bond is sp2–s
of ethene molecule, one of the sp2 hybrid
se sigma with bond length 108 pm. The H–C–H go
orbitals of carbon atom overlaps axially with
sp2 hybridised orbital of another carbon atom to
bond angle is 117.6° while the H–C–C angle
on
to form C–C sigma bond. While the other two
sp2 hybrid orbitals of each carbon atom are
egg
is 121°. The formation of sigma and pi bonds
in ethene is shown in Fig. 4.15.
tooooo
Fig. 4.15 Formation of sigma and pi bonds in ethene
124 chemistry
sp Hybridisation in C2H2 : In the formation 4.6.3 Hybridisation of Elements

of ethyne molecule, both the carbon atoms involving d Orbitals
undergo sp-hybridisation having two
30 The elements present in the third period
Sa Ba
unhybridised orbital i.e., 2py and 2px.
One sp hybrid orbital of one carbon atom
contain d orbitals in addition to s and p
Ba
orbitals. The energy of the 3d orbitals are
comparable to the energy of the 3s and 3p
overlaps axially with sp hybrid orbital of the se
sa
orbitals. The energy of 3d orbitals are also
Spree
other carbon atom to form C–C sigma bond,
while the other hybridised orbital of each By
comparable to those of 4s and 4p orbitals.
As a consequence the hybridisation involving
carbon atom overlaps axially with the half either 3s, 3p and 3d or 3d, 4s and 4p is
008
filled s orbital of hydrogen atoms forming
B
σ bonds. Each of the two unhybridised p
possible. However, since the difference in
energies of 3p and 4s orbitals is significant, no
g
orbitals of both the carbon atoms overlaps B Aa Bh
hybridisation involving 3p, 3d and 4s orbitals
Aaa
is possible.
Mens
sidewise to form two π bonds between the
boo
carbon atoms. So the triple bond between the
two carbon atoms is made up of one sigma
The important hybridisation schemes
andBelles
say
two pi bonds as shown in Fig. 4.16.
involving s, p and d orbitals are summarised
below:
Shape of
Hybridisation Atomic
molecules/ Examples
type orbitals
ions
Square dsp2 d+s+p(2) [Ni(CN)4]2–,

planar [Pt(Cl)4]2–
Trigonal sp3d s+p(3)+d PF5, PCl5
te
they
bipyramidal
Square sp3d2 s+p(3)+d(2) BrF5
t
88 Be
pyramidal
Octahedral sp3d2 s+p(3)+d(2) SF6, [CrF6]3–
d2sp3 as
d(2)+s+p(3) [Co(NH3)6]3+
(i) Formation of PCl5 (sp3d hybridisation):

The ground state and the excited state outer
electronic configurations of phosphorus
(Z=15) are represented below.
as a
Ethan
a
Mr Arenas am
Fig.4.16 Formation of sigma and pi bonds in sp3d hybrid orbitals filled by electron pairs
ethyne donated by five Cl atoms.
Now the five orbitals (i.e., one s, three six sp3d2 hybrid orbitals overlap with singly
p and one d orbitals) are available for
E Aaaa
occupied orbitals of fluorine atoms to form
I
hybridisation to yield a set of five sp3d hybrid six S–F sigma bonds. Thus SF6 molecule has
g
orbitals which are directed towards the five
corners of a trigonal bipyramidal as depicted
in the Fig. 4.17.
Boreas
a regular octahedral geometry as shown in
Fig. 4.18.
of 86 8
3,33 BE
too a
thy
sp3d2 hybridisation
Fig. 4.17 Trigonal bipyramidal geometry of PCl5

molecule
Iggy
It should be noted that all the bond angles
in trigonal bipyramidal geometry are not
equivalent. In PCl5 the five sp3d orbitals of
phosphorus overlap with the singly occupied
p orbitals of chlorine atoms to form five P–Cl
sigma bonds. Three P–Cl bond lie in one
to
plane and make an angle of 120° with each
egg
other; these bonds are termed as equatorial
bonds. The remaining two P–Cl bonds–one
Dot Fig. 4.18 Octahedral geometry of SF6 molecule
Dt
lying above and the other lying eggs below the
tag
equatorial plane, make an angle of 90° with 4.7 MOLECULAR ORBitAL tHEORy
go
the plane. These bonds are called axial bonds.
Tape
As the axial bond pairs suffer more repulsive
Molecular orbital (MO) theory was developed
by F. Hund and R.S. Mulliken in 1932. The
safe
interaction from the equatorial bond pairs, salient features of this theory are :
therefore axial bonds have been found to (i) The electrons in a molecule are present
be slightly longer and hence slightly weaker
to Bts in the various molecular orbitals as the
toB
MATE
than the equatorial bonds; which makes PCl5
molecule more reactive.
electrons of atoms are present in the
various atomic orbitals.
(ii) Formation of SF6 (sp3d2 hybridisation):
In SF6 the central sulphur atom has the (ii) The atomic orbitals of comparable
ground state outer electronic configuration
3s23p4. In the exited state the available six
togs
energies and proper symmetry combine
toe
to form molecular orbitals.
NAME
orbitals i.e., one s, three p and two d are
egg (iii) While an electron in an atomic orbital
so
singly occupied by electrons.
Eg
Eg These orbitals is influenced by one nucleus, in a
hybridise to form six new sp 3 d 2 hybrid to
molecular orbital it is influenced by
Mt
orbitals, which are projected towards the six two or more nuclei depending upon the
corners of a regular octahedron in SF6. These joy
number of atoms in the molecule. Thus,
offset
126 chemistry
an atomic orbital is monocentric while ψA and ψB. Mathematically, the formation of

a molecular orbital is polycentric. molecular orbitals may be described by the
(iv)
gtf
The number of molecular orbital formed
is equal to the number of combining
linear combination of atomic orbitals that can
take place by addition and by subtraction of
wave functions of individual atomic orbitals
atomic orbitals. When two atomic
Fog
orbitals combine, two molecular orbitals as shown below :
Boa
are formed. One is known as bonding ψMO = ψA + ψB
Maggs
molecular orbital while the other is Therefore, the two molecular orbitals
called antibonding molecular orbital. σ and σ* are formed as :
(v)
Got
The bonding molecular orbital has
lower energy and hence greater stability
togas
than the corresponding antibonding
molecular orbital.
σ = ψA + ψB
σ* = ψA – ψB
The molecular orbital σ formed by the
(vi) Just as the electron probability a

addition of atomic orbitals is called the bonding
molecular orbital while the molecular orbital
distribution around a nucleus in an σ* formed by the subtraction of atomic orbital
atom is given by an atomic orbital, the on
is called antibonding molecular orbital as
electron probability distribution around depicted in Fig. 4.19.
a group of nuclei in a molecule is given
by a molecular orbital.
(vii) The molecular orbitals like atomic
orbitals are filled in accordance with
the aufbau principle obeying the Pauli’s
exclusion principle and the Hund’s rule.
4.7.1 Formation of Molecular Orbitals

Linear Combination of Atomic
Orbitals (LCAO)
MMMEgg σ* = ψA – ψB
DESBEE
According to wave mechanics, the atomic ψA ψB
orbitals can be expressed by wave functions
aug
(ψ ’s) which represent the amplitude of the
electron waves. These are obtained from
σ = ψA + ψB
the solution of Schrödinger wave equation.

However, since it cannot be solved for any
system containing more than one electron,
Bates
molecular orbitals which are one electron
wave functions for molecules are difficult Fig.4.19 Formation of bonding (σ) and antibonding
to obtain directly from the solution of (σ*) molecular orbitals by the linear
Schrödinger wave equation. To overcome combination of atomic orbitals ψA and
this problem, an approximate method known ψB centered on two atoms A and B
respectively.
IINN
as linear combination of atomic orbitals
geftses
(LCAO) has been adopted.
Qualitatively, the formation of molecular
Let us apply this method to the orbitals can be understood in terms of the
homonuclear diatomic hydrogen molecule. constructive or destructive interference of the
Consider the hydrogen molecule consisting electron waves of the combining atoms. In the
of two atoms A and B. Each hydrogen atom formation of bonding molecular orbital, the
in the ground state has one electron in 1s two electron waves of the bonding atoms
orbital. The atomic orbitals of these atoms reinforce each other due to constructive
may be represented by the wave functions interference while in the formation of
antibonding molecular orbital, the electron as the molecular axis. It is important to note
038
waves cancel each other due to destructive that atomic orbitals having same or nearly
DooSe
interference. As a result, the electron density in the same energy will not combine if they do
a bonding molecular orbital is located between not have the same symmetry. For example,
the nuclei of the bonded atoms because of too
2pz orbital of one atom can combine with 2pz
NE
which the repulsion between the nuclei is very orbital of the other atom but not with the 3g
2px or 2py orbitals because of their different
FEE
less while in case of an antibonding molecular
orbital, most of the electron density is located symmetries.
away from the space between the nuclei. 3. the combining atomic orbitals must
t
Infact, there is a nodal plane (on which the
electron density is zero) between the nuclei 3oz_
overlap to the maximum extent. Greater
the extent of overlap, the greater will be the
the
and hence the repulsion between the nuclei is electron-density between the nuclei of a
high. Electrons placed in a bonding molecular molecular orbital.
orbital tend to hold the nuclei together and
stabilise a molecule. Therefore, a bonding 4.7.3 types of Molecular Orbitals
on
molecular orbital always possesses lower Molecular orbitals of diatomic molecules are
gy
energy than either of the atomic orbitals that designated as σ (sigma), π (pi), δ (delta), etc.
have combined to form it. In contrast, the In this nomenclature, the sigma ( )
Et__z__ atda_
electrons placed in the antibonding molecular molecular orbitals are symmetrical around
orbital destabilise the molecule. This is
because the mutual repulsion of the electrons __e the bond-axis while pi ( ) molecular orbitals
are not symmetrical. For example, the linear
in this orbital is more than the attraction
too
between the electrons and the nuclei, which
combination of 1s orbitals centered on two
nuclei produces two molecular orbitals which
causes a net increase in energy.
tog are symmetrical around the bond-axis. Such
It may be noted that the energy of the molecular orbitals are of the σ type and are
antibonding orbital is raised above the designated as σ1s and σ*1s [Fig. 4.20(a), page
FEE
energy of the parent atomic orbitals that 124]. if internuclear axis is taken to be in
have combined and the energy of the bonding the z-direction, it can be seen that a linear
g__
EgaaaagaEENNEEEg_go
of
orbital has been lowered than the parent combination of 2pz- orbitals of two atoms
orbitals. The total energy of two molecular also produces two sigma molecular orbitals
orbitals, however, remains the same as that designated as 2pz and *2pz. [Fig. 4.20(b)]
of two original atomic orbitals. Molecular orbitals obtained from 2px and
2py orbitals are not symmetrical around the
4.7.2 Conditions for the Combination of
Atomic Orbitals
Dog
bond axis because of the presence of positive
The linear combination of atomic orbitals to lobes above and negative lobes below the
form molecular orbitals takes place only if the molecular plane. Such molecular orbitals,
following conditions are satisfied: are labelled as π and =π * [Fig. 4.20(c)]. A
π bonding MO has larger electron density
tE___t.ee
1. the combining atomic orbitals must
odo_
INMNEE
have the same or nearly the same energy.
This means that 1s orbital can combine with
above and below the inter-nuclear axis. The
π* antibonding MO has a node between the
nuclei.
another 1s orbital but not with 2s orbital
because the energy of 2s orbital is appreciably 4.7.4 Energy Level Diagram for Molecular
higher than that of 1s orbital. This is not true Orbitals
if the atoms are very different. We have seen that 1s atomic orbitals on two
2. the combining atomic orbitals must atoms form two molecular orbitals designated
NEEgEEEEEE_____
have the same symmetry about the
molecular axis. By convention z-axis is taken
as σ1s and σ*1s. In the same manner, the 2s
and 2p atomic orbitals (eight atomic orbitals
128 chemistry
tee
egg
tag
Bo
or
tag
step
Fig. 4.20 Contours and energies of bonding and antibonding molecular orbitals formed through
combinations of (a) 1s atomic orbitals; (b) 2pz atomic orbitals and (c) 2px atomic orbitals.
on two atoms) give rise to the following eight The energy levels of these molecular
molecular orbitals: orbitals have been determined experimentally
from spectroscopic data for homonuclear
Antibonding
IFENG.to
MOs σ∗2s σ∗2pz π∗2px π∗2py oats
diatomic molecules of second row elements
Bonding MOs
Murphy
σ2s σ2p π2p π2p
z x y of the periodic table. The increasing order of
to
energies of various molecular orbitals for O2 The rules discussed above regarding the
and F2 is given below: stability of the molecule can be restated in
terms of bond order as follows: A positive bond
1s <  ∗1s <I  2s <  ∗2s < 2pz < (π 2px=π 2py)
o footed
Éea
T order (i.e., Nb > Na) means a stable molecule
< (π ∗2px= π∗ 2py) <  ∗2pz while a negative (i.e., Nb<Na) or zero (i.e.,
However, this sequence of energy levels egg
N b = N a) bond order means an unstable
of molecular orbitals is not correct for the molecule.
remaining molecules Li2, Be2, B2, C2, N2. For Nature of the bond
instance, it has been observed experimentally Integral bond order values of 1, 2 or 3
that for molecules such as B2, C2, N2, etc. correspond to single, double or triple bonds
the increasing order of energies of various ear as go
respectively as studied in the classical
molecular orbitals is concept.
1s <  ∗1s < 2s <  ∗2s < (π 2 px = π 2 py)
NES
< 2pz < (π ∗2px =π∗2py) <  ∗2pz
Bond-length
The bond order between two atoms in a
The important characteristic feature molecule may be taken as an approximate
of this order is that the energy of 2p z measure of the bond length. The bond length
eagL goesoo
molecular orbital is higher than that decreases as bond order increases.
of 2px and 2py molecular orbitals. Magnetic nature
4.7.5 Electronic Configuration and If all the molecular orbitals in a molecule are
Molecular Behaviour doubly occupied, the substance is diamagnetic
Its
(repelled by magnetic field). However if one or
The distribution of electrons among various 33Mt
more molecular orbitals are singly occupied it
NN
molecular orbitals is called the electronic
is paramagnetic (attracted by magnetic field),
N
configuration of the molecule. From the
_NN_z_ET
electronic configuration of the molecule, it is
tooooo
e.g., O2 molecule.
possible to get important information about 4.8 BOnDinG in SOME HOMOnUCLEAR
the molecule as discussed below. DiAtOMiC MOLECULES
Stability of Molecules: If Nb is the number In this section we shall discuss bonding in
of electrons occupying bonding orbitals and some homonuclear diatomic molecules.
Na the number occupying the antibonding
1. Hydrogen molecule (H2 ): It is formed by
orbitals, then
the combination of two hydrogen atoms. Each
(i) the molecule is stable if Nb is greater
than Na, and __ gtfo
hydrogen atom has one electron in 1s orbital.
og
Therefore, in all there are two electrons in
(ii) the molecule is unstable if Nb is less hydrogen molecule which are present in σ1s
than Na. Tt molecular
0
at
orbital. So electronic configuration
33
of hydrogen molecule is
In (i) more bonding orbitals are occupied
H2 : (σ1s)2
and so the bonding influence is stronger and a
4 t
an
stable molecule results. In (ii) the antibonding
influence is stronger and therefore the
The bond order of H2 molecule can be
calculated as given below:
age
molecule is unstable. N b  Na 2  0
egg
Bond order Bond order =  1
2 2
Bond order (b.o.) is defined as one half the This means that the two hydrogen atoms
00 8
difference between the number of electrons are bonded together by a single covalent bond.
present in the bonding and the antibonding 0
The bond dissociation energy of hydrogen
FEEL
orbitals i.e., molecule has been found to be 438 kJ mol–1
Bond order (b.o.) = ½ (N –N )
sooo b a 3
and bond length equal to 74 pm. Since no
130 chemistry
unpaired electron is present in hydrogen vapour phase. It is important to note that

molecule, therefore, it is diamagnetic. double bond in C2 consists of both pi bonds
2. Helium molecule (He2 ): The electronic
8
because of the presence of four electrons in
two pi molecular orbitals. In most of the other
configuration of helium atom is 1s2. Each
BE
helium atom contains 2 electrons, therefore,
ated
II
molecules a double bond is made up of a
sigma bond and a pi bond. In a similar fashion
in He2 molecule there would be 4 electrons.
Be
These electrons will be accommodated in
too to
the bonding in N2 molecule can be discussed.
σ1s and σ*1s molecular orbitals leading to 5. Oxygen molecule (O2 ): The electronic
Bon Ees
electronic configuration: configuration of oxygen atom is 1s2 2s2 2p4.
Each oxygen atom has 8 electrons, hence,
He2 : (σ1s)2 (σ*1s)2
C in O2 molecule there are 16 electrons. The
team
Bond order of He2 is ½(2 – 2) = 0
He2 molecule is therefore unstable and
electronic configuration of O 2 molecule,
therefore, is
does not exist.

Iff
O 2 : (1s) 2 ( ∗1s) 2 ( 2s) 2 ( ∗ 2s) 2 (2p z) 2
Similarly, it can be shown that Be2 molecule
(σ1s)2 (σ*1s)2 (σ2s)2 (σ*2s)2 also does not exist.
tee
te e
(π2px2 ≡ π2py2) (π∗2p1x ≡ π ∗2py1)
3. Lithium molecule (Li ): The electronic

2
configuration of lithium is 1s2, 2s1. There O2 : go
are six electrons in Li 2 . The electronic
configuration of Li2 molecule, therefore, is
oooooo
From the electronic configuration of O2
molecule it is clear that ten electrons are
Li2 : (σ1s)2 (σ*1s)2 (σ2s)2 t orbitals and six
oog
The above configuration is also written
present in bonding molecular
se
electrons are present in antibonding molecular
as KK(σ2s)2 where KK represents the closed orbitals. Its bond order, therefore, is
to
K shell structure (σ1s)2 (σ*1s)2.
ios
From the electronic configuration of Li2
molecule it is clear that there are four electrons
MBE
Bond order = [Nb – Na] =
Boggan
[10 – 6] =2
So in oxygen molecule, atoms are held

present in bonding molecular orbitals and two
are
electrons present in antibonding molecular
orbitals. Its bond order, therefore, is ½ (4 –
mile
by a double bond. Moreover, it may be noted
that it contains two unpaired electrons in
idgaf
π ∗2px and π ∗2py molecular orbitals, therefore,
ooo
2) = 1. It means that Li2 molecule is stable
and since it has no unpaired electrons it
oak
O 2 molecule should be paramagnetic,
ooo
tags
a prediction that corresponds to
should be diamagnetic. Indeed diamagnetic
experimental observation. In this way, the
Li 2 molecules are known to exist in the
theory successfully explains the paramagnetic
vapour phase.
Mogo
4. Carbon molecule (C2 ): The electronic
nature of oxygen.
configuration of carbon is 1s2 2s2 2p2. There Similarly, the electronic configurations
of other homonuclear diatomic molecules of []
are twelve electrons in C2. The electronic
the second row of the periodic table can be
configuration of C2 molecule, therefore, is
written. In Fig. 4.21 are given the molecular
C2 : (1s)2 ( ∗1s)2 ( ∗ 2s)2 (π2p2x = π2p2y) orbital occupancy and molecular properties
0ft for B2 through Ne2. The sequence of MOs and
as
gy.ee
or KK (2s)2 ( ∗ 2s)2 (π2p2x = π2p2y)
NNNMNEEN
The bond order of C2 is ½ (8 – 4) = 2
their electron population are shown. The bond
energy, bond length, bond order, magnetic
and C2 should be diamagnetic. Diamagneticggo properties and valence electron configuration
C2 molecules have indeed been detected in appear below the orbital diagrams.
pFpt FEBE
Fig. 4.21 MO occupancy and molecular properties for B2 through Ne2.
4.9 HyDROGEn BOnDinG Hydrogen bond is represented by a dotted

Nitrogen, oxygen and fluorine are the highly
tag
line (– – –) while a solid line represents the
covalent bond. thus, hydrogen bond can be
electronegative elements. When they are
Mth 0000
defined as the attractive force which binds
attached to a hydrogen atom to form covalent Fat
hydrogen atom of one molecule with the
bond, the electrons of the covalent bond are
shifted towards the more electronegative
i
atom. This partially positively charged
t se
electronegative atom (F, O or n) of another
molecule.
a E
hydrogen atom forms a bond with the other
tEE_fy
4.9.1 Cause of Formation of Hydrogen
more electronegative atom. This bond is Bond
known as hydrogen bond and is weaker
IES
than the covalent bond. For example, in HF When hydrogen is bonded to strongly
electronegative element ‘X’, the electron pair
izard
molecule, the hydrogen bond exists between
shared between the two atoms moves far
Esses
hydrogen atom of one molecule and fluorine
atom of another molecule as depicted below : away from hydrogen atom. As a result the
0ft
hydrogen atom becomes highly electropositive
– – – Hδ+–Fδ– – – –Hδ+ – Fδ– – – – Hδ+ – Fδ– Iggy
with respect to the other atom ‘X’. Since
Here, hydrogen bond acts as a bridge between there is displacement of electrons towards
two atoms which holds one atom by covalent X, the hydrogen acquires fractional positive
Ii at
D
bond and the other by hydrogen bond.
sea
charge (δ +) while ‘X’ attain fractional negative
132 chemistry
charge (δ–). This results in the formation of a H-bond in case of HF molecule, alcohol or
polar molecule having electrostatic force of water molecules, etc.to to
Bots
top
3
attraction which can be represented as: (2) Intramolecular hydrogen bond : It is
formed when hydrogen atom is in between
Hδ+ – Xδ– – – – Hδ+ – Xδ– – – – Hδ+ – Xδ– to
the two highly electronegative (F, O, N)
gas's
atoms present within the same molecule. For
The magnitude of H-bonding depends
on the physical state of the compound. It is
team
example, in o-nitrophenol the hydrogen is in
pedate
maximum in the solid state and minimum in between the two oxygen atoms.
the gaseous state. Thus, the hydrogen bonds
have strong influence on the structure and
properties of the compounds.
4.9.2 types of H-Bonds
There are two types of H-bonds
(i) Intermolecular hydrogen bond
joogoo f
(ii) Intramolecular hydrogen bond
(1) Intermolecular hydrogen bond : It is
formed between two different molecules of the Fig. 4.22 Intramolecular hydrogen bonding in
same or different compounds. For example, o-nitrophenol molecule
e r
SUMMARy
Kössel’s first insight into the mechanism of formation of electropositive and electronegative
ions related the process to the attainment of noble gas configurations by the respective ions.
Electrostatic attraction between ions is the cause for their stability. This gives the concept
of electrovalency.
te
The first description of covalent bonding was provided by Lewis in terms of the sharing
Ed
of electron pairs between atoms and he related the process to the attainment of noble gas
configurations by reacting atoms as a result of sharing of electrons. The Lewis dot symbols
show the number of valence electrons of the atoms of a given element and Lewis dot structures
show pictorial representations of bonding in molecules.
An ionic compound is pictured as a three-dimensional aggregation of positive and negative
ions in an ordered arrangement called the crystal lattice. In a crystalline solid there is a
charge balance between the positive and negative ions. The crystal lattice is stabilized by
the enthalpy of lattice formation.
as
While a single covalent bond is formed by sharing of an electron pair between two atoms,
multiple bonds result from the sharing of two or three electron pairs. Some bonded atoms
have additional pairs of electrons not involved in bonding. These are called lone-pairs of
electrons. A Lewis dot structure shows the arrangement of bonded pairs and lone pairs around
each atom in a molecule. important parameters, associated with chemical bonds, like:
bond length, bond angle, bond enthalpy, bond order and bond polarity have significant
effect on the properties of compounds.
A number of molecules and polyatomic ions cannot be described accurately by a single
Lewis structure and a number of descriptions (representations) based on the same skeletal
structure are written and these taken together represent the molecule or ion. This is a very
important and extremely useful concept called resonance. The contributing structures
e
or canonical forms taken together constitute the resonance hybrid which represents the
molecule or ion.
The VSEPR model used for predicting the geometrical shapes of molecules is based on
the assumption that electron pairs repel each other and, therefore, tend to remain as far
apart as possible. According to this model, molecular geometry is determined by repulsions
between lone pairs and lone pairs; lone pairs and bonding pairs and bonding pairs and bonding
pairs. The order of these repulsions being : lp-lp > lp-bp > bp-bp
__EENN2
The valence bond (vB) approach to covalent bonding is basically concerned with the
energetics of covalent bond formation about which the Lewis and VSEPR models are silent.
Basically the VB theory discusses bond formation in terms of overlap of orbitals. For example
the formation of the H2 molecule from two hydrogen atoms involves the overlap of the 1s
orbitals of the two H atoms which are singly occupied. It is seen that the potential energy
of the system gets lowered as the two H atoms come near to each other. At the equilibrium
NT
___
inter-nuclear distance (bond distance) the energy touches a minimum. Any attempt to bring
the nuclei still closer results in a sudden increase in energy and consequent destabilization
of the molecule. Because of orbital overlap the electron density between the nuclei increases
which helps in bringing them closer. It is however seen that the actual bond enthalpy and
bond length values are not obtained by overlap alone and other variables have to be taken
into account.
For explaining the characteristic shapes of polyatomic molecules Pauling introduced the
concept of hybridisation of atomic orbitals. sp, sp2, sp3 hybridizations of atomic orbitals
_____N
of Be, B, C, N and O are used to explain the formation and geometrical shapes of molecules
like BeCl2, BCl3, CH4, NH3 and H2O. They also explain the formation of multiple bonds in
molecules like C2H2 and C2H4.
The molecular orbital (MO) theory describes bonding in terms of the combination and
arrangment of atomic orbitals to form molecular orbitals that are associated with the molecule
as a whole. The number of molecular orbitals are always equal to the number of atomic
orbitals from which they are formed. Bonding molecular orbitals increase electron density
between the nuclei and are lower in energy than the individual atomic orbitals. Antibonding
molecular orbitals have a region of zero electron density between the nuclei and have more
egg
energy than the individual atomic orbitals.
The electronic configuration of the molecules is written by filling electrons in the molecular
orbitals in the order of increasing energy levels. As in the case of atoms, the Pauli exclusion
principle and Hund’s rule are applicable for the filling of molecular orbitals. Molecules are
said to be stable if the number of elctrons in bonding molecular orbitals is greater than that
in antibonding molecular orbitals.
to
Hydrogen bond is formed when a hydrogen atom finds itself between two highly
electronegative atoms such as F, O and N. It may be intermolecular (existing between two
or more molecules of the same or different substances) or intramolecular (present within
the same molecule). Hydrogen bonds have a powerful effect on the structure and properties
of many compounds.
EXERCiSES
4.1 Explain the formation of a chemical bond.

4.2 Write Lewis dot symbols for atoms of the following elements : Mg, Na, B, O, N, Br.
4.3 Write Lewis symbols for the following atoms and ions:
S and S2–; Al and Al3+; H and H–
4.4 Draw the Lewis structures for the following molecules and ions :
2−
H2S, SiCl4, BeF2, CO3 , HCOOH
4.5 Define octet rule. Write its significance and limitations.
134 chemistry
4.6 Write the favourable factors for the formation of ionic bond.
4.7 Discuss the shape of the following molecules using the VSEPR model:
BeCl2, BCl3, SiCl4, AsF5, H2S, PH3
4.8 Although geometries of NH3 and H2O molecules are distorted tetrahedral, bond angle
in water is less than that of ammonia. Discuss.
4.9 How do you express the bond strength in terms of bond order ?
4.10 Define the bond length.
2−
4.11 Explain the important aspects of resonance with reference to the CO3 ion.
4.12 H3PO3 can be represented by structures 1 and 2 shown below. Can these two
structures be taken as the canonical forms of the resonance hybrid representing
H3PO3 ? If not, give reasons for the same.
−
4.13 Write the resonance structures for SO3, NO2 and NO3 .
4.14 Use Lewis symbols to show electron transfer between the following atoms to form
cations and anions : (a) K and S (b) Ca and O (c) Al and N.
4.15 Although both CO2 and H2O are triatomic molecules, the shape of H2O molecule is
bent while that of CO2 is linear. Explain this on the basis of dipole moment.
4.16 Write the significance/applications of dipole moment.
4.17 Define electronegativity. How does it differ from electron gain enthalpy ?
4.18 Explain with the help of suitable example polar covalent bond.
4.19 Arrange the bonds in order of increasing ionic character in the molecules: LiF, K2O,
N2, SO2 and ClF3.
4.20 The skeletal structure of CH3COOH as shown below is correct, but some of the bonds
are shown incorrectly. Write the correct Lewis structure for acetic acid.
4.21 Apart from tetrahedral geometry, another possible geometry for CH4 is square planar
with the four H atoms at the corners of the square and the C atom at its centre.
Explain why CH4 is not square planar ?
4.22 Explain why BeH2 molecule has a zero dipole moment although the Be–H bonds are
polar.
4.23 Which out of NH3 and NF3 has higher dipole moment and why ?
4.24 What is meant by hybridisation of atomic orbitals? Describe the shapes of sp, sp2,
sp3 hybrid orbitals.
4.25 Describe the change in hybridisation (if any) of the Al atom in the following reaction.
AlCl 3  Cl   AlCl 4
4.26 Is there any change in the hybridisation of B and N atoms as a result of the following
reaction?
4.27 Draw diagrams showing the formation of a double bond and a triple bond between
carbon atoms in C2H4 and C2H2 molecules.
4.28 What is the total number of sigma and pi bonds in the following molecules?
(a) C2H2 (b) C2H4
4.29 Considering x-axis as the internuclear axis which out of the following will
not form a sigma bond and why? (a) 1s and 1s (b) 1s and 2px; (c) 2py and 2py
(d) 1s and 2s.
4.30 Which hybrid orbitals are used by carbon atoms in the following molecules?
CH3–CH3; (b) CH3–CH=CH2; (c) CH3-CH2-OH; (d) CH3-CHO (e) CH3COOH
4.31 What do you understand by bond pairs and lone pairs of electrons? Illustrate by
giving one exmaple of each type.
4.32 Distinguish between a sigma and a pi bond.
4.33 Explain the formation of H2 molecule on the basis of valence bond theory.
4.34 Write the important conditions required for the linear combination of atomic orbitals
to form molecular orbitals.
4.35 Use molecular orbital theory to explain why the Be2 molecule does not exist.
4.36 Compare the relative stability of the following species and indicate their magnetic
properties;
2−
(superoxide), O2 (peroxide)
4.37 Write the significance of a plus and a minus sign shown in representing the orbitals.
4.38 Describe the hybridisation in case of PCl5. Why are the axial bonds longer as compared
to equatorial bonds?
4.39 Define hydrogen bond. Is it weaker or stronger than the van der Waals forces?
4.40 What is meant by the term bond order? Calculate the bond order of : N2, O2, O2+
and O2–.

NOCB-NLKW-PS-chemical Bonding

Uploaded by

Copyright:

Available Formats

NOCB-NLKW-PS-chemical Bonding

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

NOCB-NLKW-PS-chemical Bonding

Uploaded by

Copyright:

Available Formats

Unit 4

CHEMiCAL BOnDinG AnD

Scientists are constantly discovering new compounds,

4.1 KÖ S S E L - L E w i S A p p R O A C H t O the number of valence electrons. This number

4.1.2 Covalent Bond

number of valence electrons. For example,

problem 4.1 each of the oxygen atoms completing the

The end O atom marked 2

neutral atom. Toooo

The electron gain enthalpy, ∆eg H, is the EBay

released in the processes is more than the

energy absorbed. thus a qualitative measure

bond length (Fig. 4.1). In the case of a covalent

bond, the contribution from each atom is

called the covalent radius of that atom.

the covalent radius is measured

H2O(g) → H(g) + OH(g); ∆aH1 = 502 kJ mol–1

Some of the other examples of resonance

problem 4.3 Fig. 4.5 Resonance in CO 2 molecule, I, II

Peter Debye, the Dutch chemist

• The valence shell is taken as a sphere As depicted in Table 4.6, in the

model is applicable to any such structure.

AB2E 4 1 Bent Theoretically the shape

AB3E 3 1 Trigonal Had there been a bp in place

Bent The shape should have been

AB4E 4 1 See- In (a) the lp is present at axial

Molecule no. of no. of Arrangement Shape Reason for the

AB3E2 3 2 T-shape In (a) the lp are at

Fig. 4.8 The potential energy curve for the

4.5.1 Orbital Overlap Concept

4.5.2 Directional properties of Bonds

The criterion of overlap, as the main factor Ba

ME ooooo 030mg used in bond formation. The phenomenon is

a result boron has three unpaired electrons. 2 1 1 1

orbital of equivalent energies and shape. There

In case of H2O molecule, the four oxygen

Fig.4.12 Formation of sp 3 hybrids by the

The structure of NH3 and H2O molecules

sp Hybridisation in C2H2 : In the formation 4.6.3 Hybridisation of Elements

Square dsp2 d+s+p(2) [Ni(CN)4]2–,

(i) Formation of PCl5 (sp3d hybridisation):

Fig. 4.17 Trigonal bipyramidal geometry of PCl5

an atomic orbital is monocentric while ψA and ψB. Mathematically, the formation of

(vi) Just as the electron probability a

4.7.1 Formation of Molecular Orbitals

the solution of Schrödinger wave equation.

unpaired electron is present in hydrogen vapour phase. It is important to note that

does not exist.

3. Lithium molecule (Li ): The electronic

So in oxygen molecule, atoms are held

4.9 HyDROGEn BOnDinG Hydrogen bond is represented by a dotted

4.1 Explain the formation of a chemical bond.

You might also like