Chemistry

Project Work
ANKIT DAS
XI 1104
KV NEIST JORHAT ASOM.
Chemistry Project Work

Chemical Bonding And

Molecular Structure
 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 observed facts.
Matter is made up of one or different type of elements. Under normal conditions
no other element exists as an independent atom in nature, except noble gases.
However, a group of atoms is found to exist together as one species having
characteristic properties. Such a group of atoms is called a molecule. Obviously
there must be some force which holds these constituent atoms together in the
molecules. The attractive force which holds various constituents (atoms, ions, etc.)
together in different chemical species is called a chemical bond. Since the
formation of chemical compounds takes place as a result of combination of atoms
of various elements in different ways, it raises many questions. Why do atoms
combine? Why are only certain combinations possible? Why do some atoms
combine while certain others do not? Why do molecules possess definite shapes?
To answer such questions different theories and concepts have been put forward
from time to time. These are Kössel-Lewis approach, Valence Shell Electron Pair
Repulsion (VSEPR) Theory, Valence Bond (VB) Theory and Molecular Orbital
(MO) Theory. The evolution of various theories of valence and the interpretation of
the nature of chemical bonds have closely been related to the developments in the
understanding of the structure of atom, the electronic coniguration 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.
4.1 KÖSSEL-LEWIS APPROACH TO CHEMICAL BONDING
In order to explain the formation of chemical bond in terms of electrons, a number
of attempts were made, but it was only in 1916 when Kössel and Lewis succeeded
independently in giving a satisfactory explanation. They were the first to provide
some logical explanation of valence which was based on the inertness of noble
gases.
Lewis pictured the atom in terms of a positively charged ‘Kernel’ (the nucleus plus
the inner electrons) and the outer shell that could accommodate a maximum of
eight electrons. He, further assumed that these eight electrons occupy the corners
of a cube which surround the ‘Kernel’. Thus the single outer shell electron of
sodium would occupy one corner of the cube, while in the case of a noble gas all
the eight corners would be occupied. This octet of electrons, represents a
particularly stable electronic arrangement. Lewis postulated that atoms achieve the
stable octet when they are linked by chemical bonds. In the case of sodium and
chlorine, this can happen by the transfer of an electron from sodium to chlorine
thereby giving the Na+ and Cl- ions. In the case of other molecules like Cl2, H2, F2,
etc., the bond is formed by the sharing of a pair of electrons between the atoms. In
the process each atom attains a stable outer octet of electrons.
Lewis Symbols: In the formation of a molecule, only the outer shell electrons take
part in chemical combination and they are known as valence electrons. The inner
shell electrons are well protected and are generally not involved in the
combination process. G.N. Lewis, an American chemist introduced simple
notations to represent valence electrons in an atom. These notations are called
Lewis symbols. For example, the Lewis symbols for the elements of second period
are as under:

Significance of Lewis Symbols : The number of dots around the symbol

represents the number of valence electrons. This number of valence electrons helps
to calculate the common or group valence of the element. The group valence of the
elements is generally either equal to the number of dots in Lewis symbols or 8
minus the number of dots or valence electrons.
Kössel, in relation to chemical bonding, drew attention to the following facts:
• In the periodic table, the highly electronegative halogens and the highly
electropositive alkali metals are separated by the noble gases;
• The formation of a negative ion from a halogen atom and a positive ion from an
alkali metal atom is associated with the gain and loss of an electron by the
respective atoms;
• The negative and positive ions thus formed attain stable noble gas electronic
configurations. The noble gases (with the exception of helium which has a duplet
of electrons) have a particularly stable outer shell configuration of eight (octet)
electrons, ns2np6.
• The negative and positive ions are stabilized by electrostatic attraction. For
example, the formation of NaCl from sodium and chlorine, according to the above
scheme, can be explained as:
Na → Na+ + e-
[Ne] 3s1 [Ne]
Cl + e- → Cl-
[Ne] 3s2 3p5 [Ne] 3s2 3p6 or [Ar]
Na+ + Cl- → NaCl or Na+Cl-
Similarly the formation of CaF2 may be shown as:
Ca → Ca2+ + 2e-
[Ar]4s2 [Ar]
F + e- → F-
[He] 2s2 2p5 [He] 2s2 2p6 or [Ne]
Ca2+ + 2F- → CaF2 or Ca2+(F- )2
The bond formed, as a result of the electrostatic attraction between the positive and
negative ions was termed as the electrovalent bond. The electrovalence is thus
equal to the number of unit charge(s) on the ion. Thus, calcium is assigned a
positive electrovalence of two, while chlorine a negative electrovalence of one.
Kössel’s postulations provide the basis for the modern concepts regarding
ion-formation by electron transfer and the formation of ionic crystalline
compounds. His views have proved to be of great value in the understanding and
systematisation of the ionic compounds. At the same time he did recognise the fact
that a large number of compounds did not fit into these concepts.
4.1.1 Octet Rule
Kössel and Lewis in 1916 developed an important theory of chemical combination
between atoms known as electronic theory of chemical bonding. According to this,
atoms can combine either by transfer of valence electrons from one atom to
another (gaining or losing) or by sharing of valence electrons in order to have an
octet in their 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 understood by considering the formation
of the chlorine molecule,Cl2. The Cl atom with electronic configuration, [Ne]3s2
3p5, is one electron short of the argon configuration. The formation of the Cl2
molecule can be understood in terms of the sharing of a pair of electrons between
the two chlorine atoms, each chlorine atom contributing one electron to the shared
pair. In the process both chlorine atoms attain the outer shell octet of the nearest
noble gas (i.e., argon).

The dots represent electrons. Such structures are referred to as Lewis dot
structures.
The Lewis dot structures can be written for other molecules also, in which the
combining atoms may be identical or different. The important conditions being
that:
• Each bond is formed as a result of sharing of an electron pair between the atoms.
• Each combining atom contributes at least one electron to the shared pair.
• The combining atoms attain the outershell noble gas configurations as a result of
the sharing of electrons.
• Thus in water and carbon tetrachloride molecules, formation of covalent bonds
can be represented as:

Thus, when two atoms share one electron pair they are said to be joined by a single
covalent bond. In many compounds we have multiple bonds between atoms. The
formation of multiple bonds envisages sharing of more than one electron pair
between two atoms. If two atoms share two pairs of electrons, the covalent bond
between them is called a double bond. For example, in the 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.
When combining atoms share three electron pairs as in the case of two
nitrogen atoms in the N2 molecule and the two carbon atoms in the ethyne
molecule, a triple bond is formed.

4.1.3 Lewis Representation of Simple Molecules (the Lewis Structures)

The Lewis dot structures provide a picture of bonding in molecules and ions in
terms of the shared pairs of electrons and the octet rule. While such a picture may
not explain the bonding and behaviour of a molecule completely, it does help in
understanding the 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 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
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 subtraction of one electron from the
total 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 NH4+ ion, one positive charge indicates the loss of one electron
from the group of neutral atoms.
• Knowing the chemical symbols of the combining atoms and having knowledge of
the skeletal structure of the compound (known or guessed intelligently), it is easy
to distribute the total number of electrons as bonding shared pairs between the
atoms in proportion to the total bonds.
• In general the least electronegative atom occupies the central position in the
molecule/ion. For example in the NF3 and CO32-, nitrogen and carbon are the
central atoms whereas fluorine and oxygen occupy the terminal positions.
• After accounting for the shared pairs of electrons for single bonds, the remaining
electron pairs are either utilized for multiple bonding or remain as the lone pairs.
The basic requirement being that each bonded atom gets an octet of electrons.
Lewis representations of a few molecules/ions are given in Table 4.1.
Table 4.1 The Lewis
Representation of Some
of some Molecules
Molecule/Ion Lewis Representation
H2
O2
O3

NF3

CO32-

HNO3

4.1.4 Formal Charge

Lewis dot structures, in general, do not 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 difference between the number of valence electrons of
that atom in an isolated or free state and the number of electrons assigned to that
atom in the Lewis structure. It is expressed as :
The counting is based on the assumption that the atom in the molecule owns one
electron of each shared pair and both the electrons of a lone pair.
Let us consider the ozone molecule (O3). The Lewis structure of O3 may be drawn
as :

The atoms have been numbered as 1, 2 and 3. The formal charge on:
• The central O atom marked 1 = 6 – 2 – 1/2 (6) = +1
• The end O atom marked 2 = 6 – 4 – 1/2 (4) = 0
• The end O atom marked 3 = 6 – 6 – 1/2 (2) = -1
Hence, we represent O3 along with the formal charges as follows:

We must understand that formal charges do not indicate real charge separation
within the molecule. Indicating the charges on the atoms in the Lewis structure
only helps in keeping track of the valence electrons in the molecule. Formal
charges help in the selection of the lowest energy structure from a number of
possible Lewis structures for a 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.
4.1.5 Limitations of the Octet Rule
The octet rule, though useful, is not universal. It is quite useful for understanding
the structures of most of the organic compounds and it applies mainly to the second
period 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 eight. This is especially the case
with elements having less than four valence electrons. Examples are LiCl, BeH2
and BCl3.
Li, Be and B have 1,2 and 3 valence electrons only. Some other such compounds
are AlCl3 and BF3
Odd-electron molecules
In molecules with an odd number of electrons like nitric oxide, NO and nitrogen
dioxide, NO and nitrogen dioxide, NO2, the octet rule is not satisfied for all the
atoms
The expanded octet
Elements in and beyond the third period of the periodic table have, apart from 3s
and 3p orbitals, 3d orbitals also available for bonding. In a number of compounds
of these elements there are more than eight valence electrons around the central
atom. This is termed as the expanded octet. Obviously the octet rule does not apply
in such cases.
Some of the examples of such compounds are: PF5, SF6, H2SO4 and a number of
coordination compounds.

Interestingly, sulphur also forms many compounds in which the octet rule is
obeyed. In sulphur dichloride, the S atom has an octet of electrons around it.

Other drawbacks of the octet theory

• It is clear that octet rule is based upon the chemical inertness of noble gases.
However, some noble gases (for example xenon and krypton) also combine with
oxygen and fluorine to form a number of compounds like XeF2, KrF2, XeOF2 etc.,
• This theory does not account for the shape of molecules.
• It does not explain the relative stability of the molecules being totally silent about
the energy of a molecule.
4.2 IONIC OR ELECTROVALENT BOND
From the Kössel and Lewis treatment of the formation of an ionic bond, it follows
that the 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.
The formation of a positive ion involves ionization, i.e., removal of electron(s)
from the neutral atom and that of the negative ion involves the addition of
electron(s) to the neutral atom.
M(g) → M+(g) + e- ; Ionization enthalpy
X(g) + e- → X - (g) ; Electron gain enthalpy
M+(g) + X -(g) → MX(s)
The electron gain enthalpy, ΔegH, is the enthalpy change (Unit 3), when a gas phase
atom in its ground state gains an electron. The electron gain process may be
exothermic or endothermic. The ionization, on the other hand, is always
endothermic. Electron affinity, is the negative of the energy change accompanying
electron gain.
Obviously ionic bonds will be formed more easily between elements with
comparatively low ionization enthalpies and elements with comparatively high
negative value of electron gain enthalpy.
Most ionic compounds have cations derived from metallic elements and anions
from non-metallic elements. The ammonium ion, NH4+ (made up of two
nonmetallic elements) is an exception. It forms the cation of a number of ionic
compounds.
Ionic compounds in the crystalline state consist of orderly three-dimensional
arrangements of cations and anions held together by coulombic interaction
energies. These compounds crystallise in different crystal structures determined by
the size of the ions, their packing arrangements and other factors. The crystal
structure of sodium chloride, NaCl (rock salt), for example is shown below.
In ionic solids, the sum of the electron gain enthalpy and the ionization enthalpy
may be positive but still the crystal structure gets stabilized due to the energy
released in the formation of the crystal lattice. For example: the ionization enthalpy
for Na+(g) formation from Na(g) is 495.8 kJ mol-1 ; while the electron gain
enthalpy for the change Cl(g) + e-→ Cl- (g) is, – 348.7 kJ mol-1 only. The sum of
the two, 147.1 kJ mol-1 is more than compensated for by the enthalpy of lattice
formation of NaCl(s) (-788 kJ mol-1). Therefore, the energy 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 enthalpy of lattice formation and
not simply by achieving octet of electrons around the ionic species 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 ionic compound into gaseous constituent
ions. For example, the lattice enthalpy of NaCl is 788 kJ mol-1. This means that
788 kJ of energy is required to separate one mole of solid NaCl into one mole of
Na+ (g) and one mole of Cl- (g) to an infinite distance.
This process involves both the attractive forces between ions of opposite charges
and the repulsive forces between ions of like charge. The solid crystal being
threedimensional; it is not possible to calculate lattice enthalpy directly from the
interaction of forces of attraction and repulsion only. Factors associated with the
crystal geometry have to be included.
4.3 BOND PARAMETERS
4.3.1 Bond Length
Bond length is defined as the equilibrium distance between the nuclei of two
bonded atoms in a molecule. Bond lengths are 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 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 approximately as the radius of an atom’s core

which is in contact with the core of an adjacent atom in a bonded situation. The
covalent radius is half of the distance between two similar atoms joined by a
covalent bond in the same molecule. The van der Waals radius represents the
overall size of the atom which includes its valence shell in a nonbonded situation.
Further, the van der Waals radius is half of the distance between two similar atoms
in separate molecules in a solid. Covalent and van der Waals radii of chlorine are
depicted in Fig.4.2
Some typical average bond lengths for single, double and triple bonds are shown in
Table 4.2. Bond lengths for some common molecules are given in Table 4.3. The
covalent radii of some common elements are listed in Table 4.4.
Table 4.2
Average Bond
Lengths for
Some
Covlent bond
Bond Type
length
O-H 96
C-H 107
N-O 136
C-O 143
C-N 143
C-C 154
C=O 121
N=O 122
C=C 133
C=N 138
 C=N 116
C≡C 120

Table 4.3 Bond

Lengths in
Some
Common
Bond
Molecule
Length(pm)
H2 (H-H) 74
F2(F-F) 144
Cl2 (Cl-Cl) 199
Br2 (Br-Br) 228
I2(I-I) 267
N2(N=N) 109
O2(O=O) 121
HF (H-F) 92
HCl (H-Cl) 127
HBr (H-Br) 116
HI (H-I) 120

Ta
ble
4.4
Co
val
ent
Ra
dii,
*rc
ov/
(p
m)
H 37
C 77(1) N 74(1) O 66(1) F 64
67(2) 65(2) 57(2) Cl 99
60 55(3)
P 110 S 104(1) Br 114
 95(2)
As 121 Se 104 I 133
Sb 141 Te 137
4.3.2 Bond Angle
It is defined as the angle between the orbitals containing bonding electron pairs
around the central atom in a molecule/complex ion. Bond angle is expressed in
degree which can be experimentally determined by spectroscopic methods. It gives
some idea regarding the distribution of orbitals around the central atom in a
molecule/complex ion and hence it helps us in determining its shape. For example
H-O-H bond angle in water can be represented as under :

4.3.3 Bond Enthalpy

It is defined as the amount of energy required to break one mole of bonds of a
particular type between two atoms in a gaseous state. The unit of bond enthalpy is
kJ mol-1. For example, the H – H bond enthalpy in hydrogen molecule is 435.8 kJ
mol-1.
H2(g) → H(g) + H(g); ΔaHΘ = 435.8 kJ mol-1
Similarly the bond enthalpy for molecules containing multiple bonds, for example
O2 and N2 will be as under :
O2 (O = O) (g) → O(g) + O(g); ΔaHΘ = 498 kJ mol-1
N2 (N ≡ N) (g) → N(g) + N(g); ΔaHΘ = 946.0 kJ mol-1
It is important that larger the bond dissociation enthalpy, stronger will be the bond
in the molecule. For a heteronuclear diatomic molecules like HCl, we have
HCl (g) → H(g) + Cl (g); ΔaHΘ = 431.0 kJ mol-1
In case of polyatomic molecules, the measurement of bond strength is more
complicated. For example in case of H2O molecule, the enthalpy needed to break
the two O – H bonds is not the same.
H2O(g) → H(g) + OH(g); ΔaH1Θ = 502 kJ mol-1
OH(g) → H(g) + O(g); ΔaH2Θ = 427 kJ mol-1
The difference in the ΔaHΘ 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 or
average bond enthalpy 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,
Average bond enthalpy = (502 + 427) / 2 = 464.5 kJ mol-1
4.3.4 Bond Order
In the Lewis description of covalent bond, the Bond Order is given by the number
of bonds between the two atoms in a molecule. The bond order, for example in
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 respectively. Similarly in CO (three
shared electron pairs between C and O) the bond order is 3. For N2, bond order is 3
and its Δa HΘ is 946 kJ mol-1; being one of the highest for a diatomic molecule.
Isoelectronic molecules and ions have identical bond orders; for example, F2 and
O2 2- have bond order 1. N2, CO and NO+ have bond order 3.
A general correlation useful for understanding the stablities of molecules is that:
with increase in bond order, bond enthalpy increases and bond length decreases.
4.3.5 Resonance Structures
It is often observed that a single Lewis structure is inadequate for the epresentation
of a molecule in conformity with its experimentally determined parameters. For
example, the ozone, O3 molecule can be equally represented by the structures I and
II shown below:
In both structures we have a O-O single bond and a O=O double bond. The normal
O-O and O=O bond lengths are 148 pm and 121 pm respectively. Experimentally
determined oxygen-oxygen bond lengths in the O3 molecule are same (128 pm).
Thus the oxygen-oxygen bonds in the O3 molecule are intermediate between a
double and a single bond. Obviously, this cannot be represented by either of the
two Lewis structures shown above.
The concept of resonance was introduced to deal with the type of difficulty
experienced in the depiction of accurate structures of molecules like O3. According
to the concept of resonance, whenever a single Lewis structure cannot describe a
molecule accurately, a number of structures with similar energy, positions of
nuclei, bonding and non-bonding pairs of electrons are taken as the canonical
structures of the hybrid which describes the molecule accurately. Thus for O3, the
two structures shown above constitute the canonical structures or resonance
structures and their hybrid i.e., the III structure represents the structure of O3more
accurately. This is also called resonance hybrid. Resonance is represented by a
double headed arrow.
Some of the other examples of resonance structures are provided by the carbonate
ion and the carbon dioxide molecule.

4.3.6 Polarity of Bonds

The existence of a hundred percent ionic or covalent bond represents an ideal
situation. In reality no bond or a compound is either completely covalent or ionic.
Even in case of covalent bond between two hydrogen atoms, there is some ionic
character.
When covalent bond is formed between two similar atoms, for example in H2, O2,
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 two identical nuclei. The bond
so formed is called nonpolar covalent bond. Contrary to this in case of a
heteronuclear molecule like HF, the shared electron pair between the two atoms
gets displaced more towards fluorine since the electronegativity of fluorine (Unit
3) is far greater than that of hydrogen. The resultant covalent bond is a polar
covalent bond.
As a result of polarisation, the molecule possesses the dipole moment (depicted
below) which can be defined as the product of the magnitude of the charge and the
distance between the centres of positive and negative charge. It is usually
designated by a Greek letter ‘μ;’. Mathematically, it is expressed as follows :
Dipole moment (μ) = charge (Q) x distance of separation (r)
Dipole moment is usually expressed in Debye units (D).The conversion factor is
1 D = 3.33564 x 10 -30 C m
where C is coulomb and m is meter.
Further dipole moment is a vector quantity and is depicted by a small arrow with
tail on the positive centre and head pointing towards the negative centre. For
example the dipole moment of HF may be represented as :

The shift in electron density is symbolised by crossed arrow ( ) above the

Lewis structure to indicate the direction of the shift.
In case of polyatomic molecules the dipole moment not only depend upon the
individual dipole moments of bonds known as bond dipoles but also on the spatial
arrangement of various bonds in the molecule. In such case, the dipole moment of
a molecule is the vector sum of the dipole moments of various bonds. For example
in H2O molecule, which has a bent structure, the two O-H bonds are oriented at an
angle of 104.50. Net dipole moment of 6.17 x 10–-30 C m (1D = 3.33564 x 10–-30 C
m) is the resultant of the dipole moments of two O-H bonds.
Peter Debye, the Dutch chemist
received Nobel prize in 1936 for
his work on X-ray diffraction and
dipole moments. The magnitude
of the dipole moment is given in
Deby units in order to honour him.

Net Dipole moment, μ = 1.85 D = 1.85 x 3.33564 x 10 -30 C m = 6.17 10 30 C m

The dipole moment in case of BeF2 is zero. This is because the two equal bond
dipoles point in opposite directions and cancel the effect of each other.

In tetra-atomic molecule, for example in BF3, the dipole moment is zero although
the B – F bonds are oriented at an angle of 120° to one another, the three bond
moments give a net sum of zero as the resultant of any two is equal and opposite to
the third.

Let us study an interesting case of NH3 and NF3 molecule. Both the molecules have
pyramidal shape with a lone pair of electrons
on nitrogen atom. Although fluorine is more electronegative than nitrogen, the
resultant dipole moment of NH3 ( 4.90 x 10–3 the orbital dipole due to lone pair is
in the same direction as the resultant dipole moment of the N – H bonds, whereas
in NF3 the orbital dipole is in the direction opposite to the resultant dipole moment
of the three N – F bonds. The orbital dipole because of lone pair decreases the
effect of the resultant N – F bond moments, which results in the low dipole
moment of NF3 as represented below :

Dipole moments of some molecules are shown in Table 4.5.

Table 4.5
Dipole
Moments of
Selected
Molecules
Types of Dipole
Example Geometry
Molecule Moment,µ(D)
Molecule
(AB)
HF 1.78 linear
HCl 1.07 linear
HBr 0.79 linear
HI 0.38 linear
H2 0 linear
Molecule
(AB2)
H2O 1.85 bent
H2S 0.95 bent
 CO2 0 linear
Molecule
(AB3)
trigonal-pyra
NH3 1.47
midal
trigonal-pyra
NF3 0.23
midal
trigonal-pyra
BF3 0
midal
Molecule
(AB4)
CH4 0 tetrahedral
CHCl3 1.04 tetrahedral
CCl4 0 tetrahedral
Just as all the covalent bonds have some partial ionic character, the ionic bonds
also have partial covalent character. The partial covalent character of ionic bonds
was discussed by Fajans in terms of the following rules:
• The smaller the size of the cation and the larger the size of the anion, the greater
the covalent character of an ionic bond.
• The greater the charge on the cation, the greater the covalent character of the
ionic bond.
• For cations of the same size and charge, the one, with electronic configuration
(n-1)dnnso, typical of transition metals, is more polarising than the one with a noble
gas configuration, ns2 np6, typical of alkali and alkaline earth metal cations. The
cation polarises the anion, pulling the electronic charge toward itself and 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, the polarisability of the anion and the extent of
distortion (polarisation) of anion are the factors, which determine the per cent
covalent character of the ionic bond.
4.4 THE VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR)
THEORY
As already explained, Lewis concept is unable to explain the shapes of molecules.
This theory provides a simple procedure to predict the shapes of covalent
molecules. Sidgwick and Powell in 1940, proposed a simple theory based on the
repulsive interactions of the electron pairs in the valence shell of the atoms. It was
further developed and redefined by Nyholm and Gillespie (1957).
The main postulates of VSEPR theory are as follows:
• The shape of a molecule depends upon the number of valence shell electron pairs
(bonded or nonbonded) around the central atom.
• Pairs of electrons in the valence shell repel one another since their electron clouds
are negatively charged.
• These pairs of electrons tend to occupy such positions in space that minimise
repulsion and thus maximise distance between them.
• The valence shell is taken as a sphere with the electron pairs localising on the
spherical surface at maximum distance from one another.
• A multiple bond is treated as if it is a single electron pair and the two or three
electron pairs of a multiple bond are treated as a single super pair.
• Where two or more resonance structures can represent a molecule, the VSEPR
model is applicable to any such structure.
The repulsive interaction of electron pairs decrease in the order:
Lone pair (lp) – Lone pair (lp) > Lone pair (lp) – Bond pair (bp) > Bond pair (bp) –
Bond pair (bp)
Nyholm and Gillespie (1957) refined the VSEPR model by explaining the
important difference between the lone pairs and bonding pairs of electrons. While
the lone pairs are localised on the central atom, each bonded pair is shared between
two atoms. As a result, the lone pair electrons in a molecule occupy more space as
compared to the bonding pairs of electrons. This results in greater repulsion
between lone pairs of electrons as compared to the lone pair – bond pair and bond
pair – bond pair repulsions. These repulsion effects result in deviations from
idealised shapes and alterations in bond angles in molecules.
For the prediction of geometrical shapes of molecules with the help of VSEPR
theory, it is convenient to divide molecules into two categories as (i) molecules in
which the central atom has no lone pair and (ii) molecules in which the central
atom has one or more lone pairs.
Table 4.6 (page110) shows the arrangement of electron pairs about a central atom
A (without any lone pairs) and geometries of some molecules/ions of the type AB.
Table 4.7 (page 111) shows shapes of some simple molecules and ions in which the
central atom has one or more lone pairs. Table 4.8 (page 112) explains the reasons
for the distortions in the geometry of the molecule.
As depicted in Table 4.6, in the compounds of AB2, AB3, AB4, AB5 and AB6, the
arrangement of electron pairs and the B atoms around the central atom A are :
linear, trigonal planar, tetrahedral, trigonalbipyramidal and octahedral, espectively.
Such arrangement can be seen in the molecules like BF3 (AB3), CH4 (AB4) and
PCl5 (AB5) as depicted below by their ball and stick models.

The VSEPR Theory is able to predict geometry of a large number of molecules,

especially the compounds of p-block elements accurately. It is also quite
successful in determining the geometry quite-accurately even when the energy
difference between possible structures is very small. The theoretical basis of the
VSEPR theory regarding the effects of electron pair repulsions on molecular
shapes is not clear and continues to be a subject of doubt and discussion.
Table 4.6
Geometry
of
Molecules
in which the
Central
Atom has
No Lone
Pair of
Electrons
Number of
Arrangement of Molecular
electron Examples
electron pairs geometry
pairs

2 BeCl2,HgCl2

3 BF3
 4 CH4,NH+4

5 PCl5

6 SF5

Table 4.7
Shape
(geometry
) of Some
Simple
Molecules
/Ions with
Central
Ions
having
One or
more Lone
Pairs of
Electron(E
).
No. of
Molecule No. of Arrangement of
lone Shape Examples
type bonding electron pairs
pairs
 AB2E 2 1 Bent SO2,O3

AB2E 3 1 Trigonal NH3

AB2E2 2 2 Bent H2O

AB4E 4 1 See Saw SF4

AB2E2 3 2 T-shape ClF3

Square
AB5E 5 1 BrF5
pyramid

Square
AB4E2 4 2 XeF4
planar

Table 4.8
Shapes of
Molecule
s
containin
g Bond
Pair and
Lone Pair
No.
No. of
Molecule of Reason for the shape
bonding Arrangement of electrons Shape
type lone acquired
pairs
pairs
 Theoretically the shape sho
have been triangular plan
but actually it is found to
bent or v-shaped. The reas
being the lone pairbond p
AB2E 4 1 Bent
repulsion is much more
compared to the bond
pair-bond pair repulsion.So
angle is reduced to 119.5
from 120°.
Had there been a bp in plac
of lp the shape would have
been tetrahedral but one lo
pair is present and due to th
Trigonal
AB3E 3 1 repulsion between lp-bp
pyramidal
(which is more than bp-bp
repulsion) the angle betwee
bond pairs isreduced to 107
from 109.5°.
The shape should have bee
tetrahedral if there were all
but two lp are present so th
shape is distorted tetrahedr
or angular. The reason is lp
AB2E2 2 2 Bent
repulsion is more than lp-b
repulsion which is more th
bp-bp repulsion. Thus, the
angle is reduced to 104.5°
from 109.5°.
 In (a) the lp is present at ax
position so there are three
lp?bp repulsions at 90°. In(
the lp is in an equatorial
position, and there are two
AB4E 4 1 See saw lp?bp repulsions. Hence,
arrangement (b) is more
stable. The shape shown in
is described as a distorted
tetrahedron, a folded squar
a see-saw.

In (a) the lp are at equatori

position so there are less lp
repulsions as compared to
AB3E2 3 2 T-shape
others in which the lp are a
axial positions. So structur
(a) is most stable. (T-shape

4.5 VALENCE BOND THEORY

As we know that Lewis approach helps in writing the structure of molecules but it
fails to explain the formation of chemical bond. It also does not give any reason for
the difference in bond dissociation enthalpies and bond lengths in molecules like
H2 (435.8 kJ mol-1, 74 pm) and F2 (155 kJ mol-1, 144 pm), although in both the
cases a single covalent bond is formed by the sharing of an electron pair between
the respective atoms. It also gives no idea about the shapes of polyatomic
molecules.
Similarly the VSEPR theory gives the geometry of simple molecules but
theoretically, it does not explain them and also it has limited applications. To
overcome these limitations the two important theories based on quantum
mechanical principles are introduced. These are valence bond (VB) theory and
molecular orbital (MO) theory.
Valence bond theory was introduced by Heitler and London (1927) and developed
further by Pauling and others. A discussion of the valence bond theory is based on
the knowledge of atomic orbitals, electronic configurations of elements (Units 2),
the overlap criteria of atomic orbitals, the hybridization of atomic orbitals and the
principles of variation and superposition. A rigorous treatment of the VB theory in
terms of these aspects is beyond the scope of this book. Therefore, for the sake of
convenience, valence bond theory has been discussed in terms of qualitative and
non-mathematical treatment only. To start with, let us consider the formation of
hydrogen molecule which is the simplest of all molecules.
Consider two hydrogen atoms A and B approaching each other having nuclei NA
and NB and electrons present in them are represented by eA and eB. When the two
atoms are at large distance from each other, there is no interaction between them.
As these two atoms approach each other, new attractive and repulsive forces begin
to operate.
Attractive forces arise between:
(i) nucleus of one atom and its own electron that is NA – eA and NB – eB.
(ii) nucleus of one atom and electron of other atom i.e., NA – eB, NB – eA.
Similarly repulsive forces arise between
(i) electrons of two atoms like eA – eB,
(ii) nuclei of two atoms NA – NA.
Attractive forces tend to bring the two atoms close to each other whereas repulsive
forces tend to push them apart (Fig. 4.7).
Experimentally it has been found that the magnitude of new attractive force is
more than the new repulsive forces. As a result, two atoms approach each other
and potential energy decreases. Ultimately a stage is reached where the net force of
attraction balances the force of repulsion and system acquires minimum energy. At
this stage two hydrogen atoms are said to be bonded together to form a stable
molecule having the bond length of 74 pm.
Since the energy gets released when the bond is formed between two hydrogen
atoms, the hydrogen molecule is more stable than that of isolated hydrogen atoms.
The energy so released is called as bond enthalpy, which is corresponding to
minimum in the curve depicted in Fig. 4.8. Conversely, 435.8 kJ of energy is
required to dissociate one mole of H2 molecule.
H2(g) + 435.8 kJ mol-1 → H(g) + H(g)
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 orbitals undergo partial
interpenetration. This partial merging of atomic orbitals is called overlapping of
atomic orbitals which results in the pairing of electrons. The extent of overlap
decides the strength of a covalent bond. In general, greater the overlap the stronger
is the bond formed between two atoms. Therefore, according to orbital overlap
concept, the formation of a covalent bond between two atoms results by pairing of
electrons present in the valence shell having opposite spins.
4.5.2 Directional Properties of Bonds
As we have already seen the formation of covalent bond depends on the
overlapping of atomic orbitals. The molecule of hydrogen is formed due to the
overlap of 1s-orbitals of two H atoms, when they combine with each other.
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 molecule has tetrahedral shape and HCH bond angles are 109.5°?
Why is the shape of NH3 molecule pyramidal ?
The valence bond theory explains the formation and directional properties 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 two atoms come close to each other, there is overlapping of atomic orbitals.
This overlap may be positive, negative or zero depending upon the properties of
overlapping of atomic orbitals. The various arrangements of s and p orbitals
resulting in positive, negative and zero overlap are depicted in Fig. 4.9.

The criterion of overlap, as the main factor for the formation of covalent bonds
applies uniformly to the homonuclear/heteronuclear diatomic molecules and
polyatomic molecules. In the case of polyatomic molecules like CH4, NH3 and
H2O, the VB theory has to account for their characteristic shapes as well. We know
that the shapes of CH4, NH3, and H2O molecules are tetrahedral, pyramidal and
bent respectively. It would be therefore interesting to find out if these geometrical
shapes can be explained in terms of the orbital overlaps.
Let us first consider the CH4 (methane) molecule. The electronic configuration of
carbon in its ground state is [He]2s2 2p2 which in the excited state becomes [He]
2s1 2px1 2py1 2pz1. The energy required for this excitation is compensated by the
release of energy due to overlap between the orbitals of carbon and the
hydrogen.The four atomic orbitals of carbon, each with an unpaired
electron can overlap with the 1s orbitals of the four H atoms which are also singly
occupied. This will result in the formation of four C-H bonds. It will, however, be
observed that while the three p orbitals of carbon are at 90° to one another, the
HCH angle for these will also be 90°. That is three C-H bonds will be oriented at
90° to one another. The 2s orbital of carbon and the 1s orbital of H are spherically
symmetrical and they can overlap in any direction. Therefore the direction of the
fourth C-H bond cannot be ascertained. This description does not fit in with the
tetrahedral HCH angles of 109.5°. Clearly, it follows that simple atomic orbital
overlap does not account for the directional characteristics of bonds in CH4. Using
similar procedure and arguments, it can be seen that in the case of NH3 and H2O
molecules, the HNH and HOH angles should be 90°. This is in disagreement with
the actual bond angles of 107° and 104.5° in the NH3 and H2O molecules
respectively.
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 bond is formed by the end to end
(head-on) overlap of bonding orbitals along the internuclear axis. This is called as
head on overlap or axial overlap. This can be formed by any one of the following
types of combinations of atomic orbitals.
• s-s overlapping : In this case, there is overlap of two half filled s-orbitals along
the internuclear axis as shown below :

• s-p overlapping: This type of overlap occurs between half filled s-orbitals of one
atom and half filled p-orbitals of another atom.
• p – p overlapping : This type of overlap takes place between half filled p-orbitals
of the two approaching atoms.

(ii) pi(π ) bond : In the formation of π bond the atomic orbitals overlap in such a
way that their axes remain parallel to each other and perpendicular to the
internuclear axis. The orbitals formed due to sidewise overlapping consists of two
saucer type charged clouds above and below the plane of the participating atoms.

4.5.5 Strength of Sigma and pi Bonds

Basically the strength of a bond depends upon the extent of overlapping. In case of
sigma bond, the overlapping of orbitals takes place to a larger extent. Hence, it is
stronger as compared to the pi bond where the extent of overlapping occurs to a
smaller extent. Further, it is important to note that pi bond between two atoms is
formed in addition to a sigma bond. It is always present in the molecules
containing multiple bond (double or triple bonds)
4.6 HYBRIDISATION
In order to explain the characteristic geometrical shapes of polyatomic molecules
like CH4, NH3 and H2O etc., Pauling introduced the concept of hybridisation.
According to him the atomic orbitals combine to form new set of equivalent
orbitals known as hybrid orbitals. Unlike pure orbitals, the hybrid orbitals are used
in bond formation. The phenomenon is known as hybridisation which can be
defined as the process of intermixing of the orbitals of slightly different energies so
as to redistribute their energies, resulting in the formation of new set of orbitals of
equivalent energies and shape. For example when one 2s and three 2p-orbitals of
carbon hybridise, there is the formation of four new sp3 hybrid orbitals.
Salient features of hybridisation: The main features of hybridisation are as under
:
1. The number of hybrid orbitals is equal to the number of the atomic orbitals that
get hybridised.
2. The hybridised orbitals are always equivalent in energy and shape.
3. The hybrid orbitals are more effective in forming stable bonds than the pure
atomic orbitals.
4. These hybrid orbitals are directed in space in some preferred direction to have
minimum repulsion between electron pairs and thus a stable arrangement.
Therefore, the type of hybridisation indicates the geometry of the molecules.
Important conditions for hybridisation
(i) The orbitals present in the valence shell of the atom are hybridised.
(ii) The orbitals undergoing hybridisation should have almost equal energy.
(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 valence shell take part in hybridisation.
4.6.1 Types of Hybridisation
There are various types of hybridisation involving s, p and d orbitals. The different
types of hybridisation are as under:
(I) sp hybridisation: This type of hybridisation involves the mixing of one s and
one p orbital resulting in the formation of two equivalent sp hybrid orbitals. The
suitable orbitals for sp hybridisation are s and pz, if the hybrid orbitals are to lie
along the z-axis. Each sp hybrid orbitals has 50% s-character and 50% p-character.
Such a molecule in which the central atom is sp-hybridised and linked directly to
two other central atoms possesses linear geometry. This type of hybridisation is
also known as diagonal hybridisation.
The two sp hybrids point in the opposite direction along the z-axis with projecting
positive lobes and very small negative lobes, which provides more effective
overlapping resulting in the formation of stronger bonds.
Example of molecule having sp hybridisation
BeCl2: The ground state electronic configuration of Be is 1s22s2. In the exited state
one of the 2s-electrons is promoted to vacant 2p orbital to account for its divalency.
One 2s and one 2p-orbitals get hybridised to form two sp hybridised orbitals.
These two sp hybrid orbitals are oriented in opposite direction forming an angle of
180°. Each of the sp hybridised orbital overlaps with the 2p-orbital of chlorine
axially and form two Be- Cl sigma bonds. This is shown in Fig. 4.10.

(II) sp2 hybridisation : In this hybridisation there is involvement of one s and two
p-orbitals in order to form three equivalent sp2 hybridised orbitals. For example, in
BCl3 molecule, the ground state electronic configuration of central boron atom is
1s22s22p1. In the excited state, one of the 2s electrons is promoted to vacant 2p
orbital as a result boron has three unpaired electrons. These three orbitals (one 2s
and two 2p) hybridise to form three sp2 hybrid orbitals. The three hybrid orbitals so
formed are oriented in a trigonal planar arrangement and overlap with 2p orbitals
of chlorine to form three B-Cl bonds. Therefore, in BCl3 (Fig. 4.11), the geometry
is trigonal planar with ClBCl bond angle of 120°.
(III) sp3 hybridisation: This type of hybridisation can be explained by taking the
example of CH4 molecule in which there is mixing of one s-orbital and three
p-orbitals of the valence shell to form four sp3 hybrid orbital of equivalent energies
and shape. There is 25% s-character and 75% pcharacter in each sp3 hybrid orbital.
The four sp3 hybrid orbitals so formed are directed towards the four corners of the
tetrahedron. The angle between sp3 hybrid orbital is 109.5° as shown in Fig. 4.12.
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 ground state is 2s22 px1 2 py1 2 pz1 having three unpaired electrons in the sp3
hybrid orbitals and a lone pair of electrons is present in the fourth one. These three
hybrid orbitals overlap with 1s orbitals of hydrogen atoms to form three N-H sigma
bonds. We know that the force of repulsion between a lone pair and a bond pair is
more than the force of repulsion between two bond pairs of electrons. The
molecule thus gets distorted and the bond angle is reduced to 107° from 109.5°.
The geometry of such a molecule will be pyramidal as shown in Fig. 4.13.
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 four sp3 hybrid
orbitals acquire a tetrahedral geometry, with two corners occupied by hydrogen
atoms while the other two by the lone pairs. The bond angle in this case is reduced
to 104.5° from 109.5° (Fig. 4.14) and the molecule thus acquires a V-shape or
angular geometry.

4.6.2 Other Examples of sp3, sp2 and sp Hybridisation

sp3 Hybridisation in C2H6 molecule: In ethane molecule both the carbon atoms
assume sp3 hybrid state. One of the four sp3 hybrid orbitals of carbon atom
overlaps axially with similar orbitals of other atom to form sp3-sp3 sigma bond
while the other three hybrid orbitals of each carbon atom are used in forming sp3-s
sigma bonds with hydrogen atoms as discussed in section 4.6.1(iii). Therefore in
ethane C-C bond length is 154 pm and each C-H bond length is 109 pm.
sp2 Hybridisation in C2H4: In the formation of ethene molecule, one of the sp 2
hybrid orbitals of carbon atom overlaps axially with sp2 hybridised orbital of
another carbon atom to form C-C sigma bond. While the other two sp2 hybrid
orbitals of each carbon atom are used for making sp2-s sigma bond with two
hydrogen atoms. The unhybridised orbital (2px or 2py) of one carbon atom overlaps
sidewise with the similar orbital of the other carbon atom to form weak π bond,
which consists of two equal electron clouds distributed above and below the plane
of carbon and hydrogen atoms.
Thus, in ethene molecule, the carboncarbon bond consists of one sp2-sp2 sigma
bond and one pi (π ) bond between p orbitals which are not used in the
hybridisation and are perpendicular to the plane of molecule; the bond length 134
pm. The C-H bond is sp2-s sigma with bond length 108 pm. The H-C-H bond angle
is 117.6° while the H-C-C angle is 121°. The formation of sigma and pi bonds in
ethene is shown in Fig. 4.15.
sp Hybridisation in C2H2 : In the formation of ethyne molecule, both the carbon
atoms undergo sp-hybridisation having two unhybridised orbital i.e., 2py and 2px.
One sp hybrid orbital of one carbon atom overlaps axially with sp hybrid orbital of
the other carbon atom to form C-C sigma bond, while the other hybridised orbital
of each carbon atom overlaps axially with the half filled s orbital of hydrogen
atoms forming σ bonds. Each of the two unhybridised p orbitals of both the carbon
atoms overlaps sidewise to form two π bonds between the carbon atoms. So the
triple bond between the two carbon atoms is made up of one sigma and two pi
bonds as shown in Fig. 4.16.
4.6.3 Hybridisation of Elements involving d Orbitals
The elements present in the third period contain d orbitals in addition to s and p
orbitals. The energy of the 3d orbitals are comparable to the energy of the 3s and
3p orbitals. The energy of 3d orbitals are also comparable to those of 4s and 4p
orbitals. As a consequence the hybridisation involving either 3s, 3p and 3d or 3d,
4s and 4p is possible. However, since the difference in energies of 3p and 4s
orbitals is significant, no hybridisation involving 3p, 3d and 4s orbitals is possible.
The important hybridisation schemes involving s, p and d orbitals are summarised
below:
Shapes of Hybridisation Atomic
Examples
molecules/ions type orbitals
2 [Ni(CN)]2-.
Square planar dsp d+s+p(2) [Pt(Cl) ]2-
4
Trigonal
sp3d s+p(3)+d PF5.PCl5
bipyramidal
Square pyramidal sp3d2 s+p(3)+d(2) BrF5
2 2
sp d s+p(3)+d(2) SF6.[CrF6]3-[Co(NH3
Octahedral
d2sp3 d(2)+s+p(3) )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.

Now the five orbitals (i.e., one s, three p and one d orbitals) are available for
hybridisation to yield a set of five sp3d hybrid orbitals which are directed towards
the five corners of a trigonal bipyramidal as depicted in the Fig. 4.17.
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 plane and make an angle of 120° with each other; these bonds are
termed as equatorial bonds. The remaining two P-Cl bonds-one lying above and
the other lying below the equatorial plane, make an angle of 90° with the plane.
These bonds are called axial bonds. As the axial bond pairs suffer more repulsive
interaction from the equatorial bond pairs, therefore axial bonds have been found
to be slightly longer and hence slightly weaker than the equatorial bonds; which
makes PCl5 molecule more reactive.
(ii) Formation of SF2 (sp3d2 hybridisation): In SF6 the central sulphur atom has
the ground state outer electronic configuration 3s23p4. In the exited state the
available six orbitals i.e., one s, three p and two d are singly occupied by electrons.
These orbitals hybridise to form six new sp3d2 hybrid orbitals, which are projected
towards the six corners of a regular octahedron in SF6. These six sp3d2 hybrid
orbitals overlap with singly occupied orbitals of fluorine atoms to form six S-F
sigma bonds. Thus SF2 molecule has a regular octahedral geometry as shown in
Fig. 4.18.
4.7 MOLECULAR ORBITAL THEORY
Molecular orbital (MO) theory was developed by F. Hund and R.S. Mulliken in
1932. The salient features of this theory are :
(i) The electrons in a molecule are present in the various molecular orbitals as the
electrons of atoms are present in the various atomic orbitals.
(ii) The atomic orbitals of comparable energies and proper symmetry combine to
form molecular orbitals.
(iii) While an electron in an atomic orbital is influenced by one nucleus, in a
molecular orbital it is influenced by two or more nuclei depending upon the
number of atoms in the molecule. Thus, an atomic orbital is monocentric while a
molecular orbital is polycentric.
(iv) The number of molecular orbital formed is equal to the number of combining
atomic orbitals. When two atomic orbitals combine, two molecular orbitals are
formed. One is known as bonding molecular orbital while the other is called
antibonding molecular orbital.
(v) The bonding molecular orbital has lower energy and hence greater stability than
the corresponding antibonding molecular orbital.
(vi) Just as the electron probability distribution around a nucleus in an atom is
given by an atomic orbital, the electron probability distribution around 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)
According to wave mechanics, the atomic orbitals can be expressed by wave
functions (ψ ’s) which represent the amplitude of the electron waves. These are
obtained from the solution of Schrödinger wave equation. However, since it cannot
be solved for any system containing more than one electron, molecular orbitals
which are one electron wave functions for molecules are difficult to obtain directly
from the solution of Schrödinger wave equation. To overcome this problem, an
approximate method known as linear combination of atomic orbitals (LCAO) has
been adopted.
Let us apply this method to the homonuclear diatomic hydrogen molecule.
Consider the hydrogen molecule consisting of two atoms A and B. Each hydrogen
atom in the ground state has one electron in 1s orbital. The atomic orbitals of these
atoms may be represented by the wave functions ψA and ψB. Mathematically, the
formation of molecular orbitals may be described by the linear combination of
atomic orbitals that can take place by addition and by subtraction of wave
functions of individual atomic orbitals as shown below :
ψMO = ψA + ψB
Therefore, the two molecular orbitals σ and σ* are formed as :
σ = ψA + ψB
σ* = ψA – ψB
The molecular orbital σ formed by the addition of atomic orbitals is called the
bonding molecular orbital while the molecular orbital σ* formed by the subtraction
of atomic orbital is called antibonding molecular orbital as depicted in Fig. 4.19.
Qualitatively, the formation of molecular orbitals can be understood in terms of the
constructive or destructive interference of the electron waves of the combining
atoms. In the formation of bonding molecular orbital, the two electron waves of the
bonding atoms reinforce each other due to constructive interference while in the
formation of antibonding molecular orbital, the electron waves cancel each other
due to destructive interference. As a result, the electron density in a bonding
molecular orbital is located between the nuclei of the bonded atoms because of
which the repulsion between the nuclei is very less while in case of an antibonding
molecular orbital, most of the electron density is located away from the space
between the nuclei. Infact, there is a nodal plane (on which the electron density is
zero) between the nuclei and hence the repulsion between the nuclei is high.
Electrons placed in a bonding molecular orbital tend to hold the nuclei together and
stabilise a molecule. Therefore, a bonding molecular orbital always possesses
lower energy than either of the atomic orbitals that have combined to form it. In
contrast, the electrons placed in the antibonding molecular orbital destabilise the
molecule. This is because the mutual repulsion of the electrons in this orbital is
more than the attraction between the electrons and the nuclei, which causes a net
increase in energy.
It may be noted that the energy of the antibonding orbital is raised above the
energy of the parent atomic orbitals that have combined and the energy of the
bonding orbital has been lowered than the parent orbitals. The total energy of two
molecular orbitals, however, remains the same as that of two original atomic
orbitals.
4.7.2 Conditions for the Combination of Atomic Orbitals
The linear combination of atomic orbitals to form molecular orbitals takes place
only if the following conditions are satisfied:
1.The combining atomic orbitals must have the same or nearly the same energy.
This means that 1s orbital can combine with another 1s orbital but not with 2s
orbital because the energy of 2s orbital is appreciably higher than that of 1s orbital.
This is not true if the atoms are very different.
2.The combining atomic orbitals must have the same symmetry about the
molecular axis. By convention z-axis is taken as the molecular axis. It is important
to note that atomic orbitals having same or nearly the same energy will not
combine if they do not have the same symmetry. For example, 2pz orbital of one
atom can combine with 2pz orbital of the other atom but not with the 2px or 2py
orbitals because of their different symmetries.
3.The combining atomic orbitals must overlap to the maximum extent. Greater the
extent of overlap, the greater will be the electron-density between the nuclei of a
molecular orbital.
4.7.3 Types of Molecular Orbitals
Molecular orbitals of diatomic molecules are designated as σ (sigma), π (pi), δ
(delta), etc.
In this nomenclature, the sigma (σ) molecular orbitals are symmetrical around the
bond-axis while pi (π) molecular orbitals are not symmetrical. For example, the
linear combination of 1s orbitals centered on two nuclei produces two molecular
orbitals which are symmetrical around the bond-axis. Such molecular orbitals are
of the σ type and are designated as σ1s and σ*1s [Fig. 4.20(a),page 124]. If
internuclear axis is taken to be in the z-direction, it can be seen that a linear
combination of 2pz- orbitals of two atoms also produces two sigma molecular
orbitals designated as σ2pz and σ*2pz. [Fig. 4.20(b)]
Molecular orbitals obtained from 2px and 2py orbitals are not symmetrical around
the bond axis because of the presence of positive lobes above and negative lobes
below the molecular plane. Such molecular orbitals, are labelled as π and π * [Fig.
4.20(c)]. A π bonding MO has larger electron density above and below the
inter-nuclear axis. The π* antibonding MO has a node between the nuclei.
4.7.4 Energy Level Diagram for Molecular Orbitals
We have seen that 1s atomic orbitals on two atoms form two molecular orbitals
designated as σ1s and σ*1s. In the same manner, the 2s and 2p atomic orbitals
(eight atomic orbitals on two atoms) give rise to the following eight molecular
orbitals:
Antibonding MOs σ*2s σ*2pz π*2px π*2py
Bonding MOs σ2s σ2pz π2px π2py
The energy levels of these molecular orbitals have been determined experimentally
from spectroscopic data for homonuclear diatomic
molecules of second row elements of the periodic table. The increasing order of
energies of various molecular orbitals for O2 and F2 is given below :
σ1s < σ*1s < σ2s < σ*2s <σ2pz<(π 2px = π 2py)< (π *2px= π *2py)<σ*2pz
However, this sequence of energy levels of molecular orbitals is not correct for the
remaining molecules Li2, Be2, B2, C2, N2. For instance, it has been observed
experimentally that for molecules such as B2, C2, N2 etc. the increasing order of
energies of various molecular orbitals is
σ1s < σ*1s < σ2s < σ*2s < (π 2px = π 2py) <σ2pz < (π *2px= π *2py) < σ*2pz
The important characteristic feature of this order is that the energy of σ2pz
molecular orbital is higher than that of π 2px and π 2py molecular orbitals.
4.7.5 Electronic Configuration and Molecular Behaviour
The distribution of electrons among various molecular orbitals is called the
electronic configuration of the molecule. From the electronic configuration of the
molecule, it is possible to get important information about the molecule as
discussed below.
Stability of Molecules: If Nb is the number of electrons occupying bonding
orbitals and Na the number occupying the antibonding orbitals, then
(i) the molecule is stable if Nb is greater than Na, and
(ii) the molecule is unstable if Nb is less than Na.
In (i) more bonding orbitals are occupied and so the bonding influence is stronger
and a stable molecule results. In (ii) the antibonding influence is stronger and
therefore the molecule is unstable.
Bond order
Bond order (b.o.) is defined as one half the difference between the number of
electrons present in the bonding and the antibonding
orbitals i.e.,
Bond order (b.o.) = 1/2 (Nb – Na)
The rules discussed above regarding the stability of the molecule can be restated in
terms of bond order as follows: A positive bond order (i.e., Nb > Na) means a stable
molecule while a negative (i.e., Nba) or zero (i.e., Nb = Na) bond order means an
unstable molecule.
Nature of the bond
Integral bond order values of 1, 2 or 3 correspond to single, double or triple bonds
respectively as studied in the classical concept.
Bond-length
The bond order between two atoms in a molecule may be taken as an approximate
measure of the bond length. The bond length decreases as bond order increases.
Magnetic nature
If all the molecular orbitals in a molecule are doubly occupied, the substance is
diamagnetic (repelled by magnetic field). However if one or more molecular
orbitals are singly occupied it is paramagnetic (attracted by magnetic field), e.g.,
O2 molecule.
4.8 BONDING IN SOME HOMONUCLEAR DIATOMIC MOLECULES
In this section we shall discuss bonding in some homonuclear diatomic molecules.
1. Hydrogen molecule (H2 ): It is formed by the combination of two hydrogen
atoms. Each hydrogen atom has one electron in 1s orbital. Therefore, in all there
are two electrons in hydrogen molecule which are present in σ1s molecular orbital.
So electronic configuration of hydrogen molecule is
H2 : (σ1s)2
The bond order of H2 molecule can be calculated as given below:
Bond order = (Na – Nb) / 2 = (2 -0) / 2 = 1
This means that the two hydrogen atoms are bonded together by a single covalent
bond. The bond dissociation energy of hydrogen molecule has been found to be
438 kJ mol-1 and bond length equal to 74 pm. Since no unpaired electron is present
in hydrogen molecule, therefore, it is diamagnetic.
2. Helium molecule (He2 ): The electronic configuration of helium atom is 1s2.
Each helium atom contains 2 electrons, therefore, in He2 molecule there would be 4
electrons. These electrons will be accommodated in σ1s and σ*1s molecular
orbitals leading to electronic configuration:
He2: (σ1s)2 (σ*1s)2
Bond order of He2 is (2 – 2) = 0
He2 molecule is therefore unstable and does not exist.
Similarly, it can be shown that Be2 molecule (σ1s)2 (σ*1s)2 (σ2s)2 (σ*2s)2 also
does not exist.
3. Lithium molecule (Li2 ): The electronic configuration of lithium is 1s2, 2s1 .
There are six electrons in Li2. The electronic configuration of Li2 molecule,
therefore, is
Li2 : (σ1s)2 (σ*1s)2 (σ2s)2
The above configuration is also written as KK(σ2s)2 where KK represents the
closed K shell structure (σ1s)2 (σ*1s)2.
From the electronic configuration of Li2 molecule it is clear that there are four
electrons present in bonding molecular orbitals and two electrons present in
antibonding molecular orbitals. Its bond order, therefore, is 1/2 (4 – 2) = 1. It
means that Li2 molecule is stable and since it has no unpaired electrons it should be
diamagnetic. Indeed diamagnetic Li2 molecules are known to exist in the vapour
phase.
4. Carbon molecule (C2 ): The electronic configuration of carbon is 1s2 2s2 2p2.
There are twelve electrons in C2. The electronic configuration of C2 molecule,
therefore, is
C2 : (σ1s)2 (σ*1s )2(σ2s )2(σ*2s )2( π2px2 = π2py2)
or KK(σ2s)2(σ*2s)2(π2px2=π2py2)
The bond order of C2 is 1/2 (8 – 4) = 2 and C2 should be diamagnetic.
Diamagnetic C2 molecules have indeed been detected in vapour phase. It is
important to note that double bond in C2 consists of both pi bonds because of the
presence of four electrons in two pi molecular orbitals. In most of the other
molecules a double bond is made up of a sigma bond and a pi bond. In a similar
fashion the bonding in N2 molecule can be discussed.
5. Oxygen molecule (O2 ): The electronic configuration of oxygen atom is 1s2 2s2
2p4. Each oxygen atom has 8 electrons, hence, in O2 molecule there are 16
electrons. The electronic configuration of O2 molecule, therefore, is
O2 : (σ1s)2 (σ*1s )2(σ2s )2(σ*2s )2(σ2pz )2 (π2px2 ≡ π2py2)(π*2px1 ≡ π*2py1)
or KK(σ2s)2(σ*2s)2(σ2pz )2(π2px2 ≡ π2py2),(π*2px1 ≡ π*2py1)
From the electronic configuration of O2 molecule it is clear that ten electrons are
present in bonding molecular orbitals and six electrons are present in antibonding
molecular orbitals. Its bond order, therefore, is
Bond order = 1/2[Nb−Na] = 1/2[10-6] = 2
So in oxygen molecule, atoms are held by a double bond. Moreover, it may be
noted that it contains two unpaired electrons in π *2px and π *2py molecular
orbitals, therefore, O2 molecule should be paramagnetic, a prediction that
corresponds to experimental observation. In this way, the theory successfully
explains the paramagnetic nature of oxygen.
Similarly, the electronic configurations of other homonuclear diatomic molecules
of the second row of the periodic table can be written. In Fig.4.21 are given the
molecular orbital occupancy and molecular properties for B2 through Ne2. The
sequence of MOs and their electron population are shown. The bond energy, bond
length, bond order, magnetic properties and valence electron configuration appear
below the orbital diagrams.
4.9 HYDROGEN BONDING
Nitrogen, oxygen and fluorine are the higly electronegative elements. When they
are attached to a hydrogen atom to form covalent bond, the electrons of the
covalent bond are shifted towards the more electronegative atom. This partially
positively charged hydrogen atom forms a bond with the other more
electronegative atom. This bond is known as hydrogen bond and is weaker than the
covalent bond. For example, in HF molecule, the hydrogen bond exists between
hydrogen atom of one molecule and fluorine atom of another molecule as depicted
below :
− − −Hδ+ –Fδ− − − −Hδ+ –Fδ− − − −Hδ+ –Fδ−
Here, hydrogen bond acts as a bridge between two atoms which holds one atom by
covalent bond and the other by hydrogen bond. Hydrogen bond is represented by a
dotted line (− − −) while a solid line represents the covalent bond. Thus, hydrogen
bond can be defined as the attractive force which binds hydrogen atom of one
molecule with the electronegative atom (F, O or N) of another molecule.
4.9.1 Cause of Formation of Hydrogen Bond
When hydrogen is bonded to strongly electronegative element ‘X’, the electron
pair shared between the two atoms moves far away from hydrogen atom. As a
result the hydrogen atom becomes highly electropositive with respect to the other
atom ‘X’. Since there is displacement of electrons towards X, the hydrogen
acquires fractional positive charge (δ +) while ‘X’ attain fractional negative charge
(δ−). This results in the formation of a polar molecule having electrostatic force of
attraction which can be represented as :
Hδ+ − Xδ− −−− Hδ+ −Xδ− −−− Hδ+ − Xδ−
The magnitude of H-bonding depends on the physical state of the compound. It is
maximum in the solid state and minimum in 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
(ii) Intramolecular hydrogen bond
(1) Intermolecular hydrogen bond : It is formed between two different molecules
of the same or different compounds. For example, H-bond in case of HF molecule,
alcohol or water molecules, etc.
(2) Intramolecular hydrogen bond : It is formed when hydrogen atom is in
between the two highly electronegative (F, O, N) atoms present within the same
molecule. For example, in o-nitrophenol the hydrogen is in between the two
oxygen atoms.
 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.
The first description of covalent bonding was provided by Lewis in terms of the
sharing 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.
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 lonepairs 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 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
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 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 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 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.
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.
.