Chemical Bonding and Molecular Structure PDF

Chapter 2: Chemical Bonding and Molecular Structure
B.Sc (Prog.) 1st Year

Paper No:CHPT -101
Unit No :1
Chapter No and Name: 2, Chemical Bonding and Molecular Structure
Fellow: Dr. V. C. Rao, Associate Professor

Collge/Department: Sri Venkateswara College,University of Delhi
Author : Dr. Geetika Gandhi, Assistant Professor
College/Department : Hindu College, University of Delhi
Reviewer: Prof. Pawan Mathur
College/Department : Department of Chemistry, University of Delhi
Institute of Lifelong Learning, University of Delhi
2.1 Introduction
Structure and bonding lie at the heart of modern inorganic chemistry. We can deduce
from chemical evidence that atoms combine to form larger units and the stability of
these units is due to chemical bonds.
There are about 118 elements, but when the elements combine they can make a huge
number of compounds. Some of them existed when the world began. Some have been
made by men and women, either by accident or design. Bonding is a consequesnce of
interaction of electrons in the outermost shells of atomic or ionic species involved.
In this chapter, we shall encounter methods of explaining and predicting the bonding in
a variety of compounds.
Why do chemical bonds form?
Chemical bonds form if the resulting arrangement of the atoms has lower energy than
the separated atoms i.e., atoms combine to attain a state of lower energy (potential)
than that in the isolated ones, e.g. H2, P4, S8, H2O, C6H12O6 etc.
Various changes in energy that occur when bonds form results from the movement of
the valence electrons (the electrons in the outermost shell) of atoms.
What holds atoms together in chemical compounds?
The forces that hold atoms together are called chemical bonds. A chemical bond is a
manifestation of a force of attraction.
What is the nature of chemical bonds?
Atoms combine in a variety of ways. Mainly, three different types of bonds may be
formed, depending on the electropositive or electronegative character of the atoms
involved.
Ionic bond
It involves the complete transfer of one or more electrons from one atom to another and
is characterized by a large difference in electronegativity. An ionic bond is formed
between an electropositive and an electronegative element.
Covalent bond
It involves the sharing of a pair of electrons between two atoms and is characterized by
a small difference in electronegativity. A covalent bond is formed between two
electronegative elements or could be generated between a less electropositive and an
electronegative element.
Metallic bond
It involves the free movement of valence electrons throughout the crystal and is also
characterized by small difference in electronegativity. A metallic bond is formed between
two electropositive elements.
Classification of chemical bonds based on the types of forces that hold the atoms
together as shown in Fig. 2.1.

Figure 2.1: Classification of chemical bonds based on the type of forces that hold the
atoms
Examples :
(i) Ionic bond
(ii) Metallic bond
(iii) Hydrogen bond
(iv) Dipolar
(v) Polar covalent bond
(vi) Nonpolar covalent bond
a. simple molecules
b. giant molecules
NaCl, CaO
Na, Cu, Alloys
(NH3)n (H2O)n, (HF)n
(NF3)n
HF, H2O
H2, Cl2
C (diamond), SiC
2.2 Preliminary Survey

Classical theory
In 1916, W. Kossel from Germany and G. N. Lewis from U.S. independently proposed
theories of chemical bonding on the basis of the developments in the area of atomic
structure. It was termed as electronic theory of valency. They attempted to explain the
nature of bonds in ionic and nonpolar molecules.
A Lewis structure is a representation of covalent bonding using Lewis dot symbols in
which shared electron pairs are shown either as lines or as pairs of dots between two
atoms and lone pairs are shown as pairs of dots on individual atoms. Only valence
electrons are shown in a Lewis structure. In covalent bond formation, atoms go as far
as possible towards completing their octets by sharing electron pairs.
Lewis
octet rule:
Each atom shares electrons with neighbouring atoms to achieve a total of eight
valence electrons.
Lewis
electron-dot diagrams provide a good starting point for analysing the bonding in
molecules.
These diagrams show the number of bonds between specific atoms and the resonance
possibilities. A few examples of Lewis structures are given in Fig. 2.2.
Figure 2.2: Lewis structures

Limitations of octet rule
The octet rule, though useful, is not universal.
It fails to account for the stability of
(i) the molecules with incomplete octet on the central atom (BeCl2, BCl3)
(ii) the molecules with expanded octet (PF5, SF6)
(iii) odd-electron molecules (NO, NO2)
It cannot account for the shape of a molecule (CO2 linear, SO2 bent).
It does not mention anything regarding the relative stability of a molecule.
Summarily, it may be concluded that the electronic theory of valence and the octet
rule are empirical in nature.
Modern theories
description of bonding must be consistent with experimental data on bond
Any
lengths, bond angles and bond strengths.
Application
of the quantum-mechanical approaches provide quantitative

understanding of the mechanisms of energy lowering in terms of electron behaviour.

The
number of atoms in a molecule, their ordering, their relative spacing, and the
overall molecular shape are all fixed because the energy of the molecule is minimum
(relative to isolated atoms) only for a particular number and arrangement of the
constituent atoms.
The magnitude of the bond energy is a measure of the strength of the bond.
Biographich Sketch
2.3 Ionic Bonding (Electrovalent Bonding)
The first explanation of chemical bonding was suggested by the properties of salts,
substances now known to be ionic. The ionic bond is a consequence of electrostatic
interaction between the oppositely charged ions that result from the transfer of one or
more electrons from a less electronegative atom to a more electronegative atom. The
atom that loses electrons becomes cation (positive ion), the atom that gains electrons
becomes an anion (negative ion). Any given ion tends to attract as many neighbouring
ions of opposite charge as possible. The formation of solid sodium chloride from sodium
atom and chlorine atom is shown in Fig. 2.3.
Figure 2.3: Formation of Na+Cl- solid from sodium atom and chlorine atom
M (g) M+ (g) + eX (g) + e- X- (g)
M+ (g) + X- (g) MX (s)
Ionization enthalpy
Electron gain enthalpy
Lattice enthalpy
Ionic bonds will be formed more easily between elements with comparatively low
ionization enthalpies and elements with comparatively high electron gain enthalpies.
We can represent electron transfer by the following equation
Na ([Ne] 3s1) + Cl ([Ne] 3s2 3p5) Na+ ([Ne]) + Cl- ([Ne] 3s2 3p6)
As a result of the electron transfer, ions are formed, each of which has a noble gas
configuration.
Characteristics of ionic solids
Ionic compounds usually exist as crystalline solids. X-ray diffraction patterns of

the electrovalent compounds have revealed that the constituent parts of the
crystals are ions.
Ionic bond is non-directional.
Ionic bonds are quite strong and hence ionic compounds have high melting
point/boiling point and are hard and brittle.
Ionic compounds tend to have very low electrical conductivity as solids but
conduct electricity quite well when molten or dissolved in water. This conductivity
is attributed to the presence of oppositely charged ions, which are free to move
under the influence of an electric field.
Ionic compounds are soluble in polar solvents like water and insoluble in nonpolar
solvents like benzene and carbon tetrachloride.
Structure of ionic solids

Ionic solids consist of positive and negative ions arranged in a manner so as to acquire
minimum potential energy.
The most stable arrangement is the one in which the ions are in contact with
each other and arranged in a symmetrical manner (close packed geometry).
Lattice coordination number is the number of immediate neighbouring oppositely
charged ions.
The size factors largely determine the geometry of the structures and
coordination number.
The radius ratio

accounts for the geometry of many ionic solids (Table
2.1).
A large number of ionic solids exhibit one of the following structures.
i.
rock salt type, NaCl
ii.
wurzite, ZnS
iii.
zinc blende, ZnS
iv.
fluorite, CaF2
v.
anti fluorite, CsCl
vi.
rutile, TiO2
Table 2.1 Radius Ratio and Geometry of Ionic Solids

Anion
Coordination
Limiting radius ratio,
Arrangement
Number
Examples
Uncommon among
ionic solids
Uncommon among
ionic solids
Linear
0 - 0.155
Triangular
0.155 - 0.225
Tetrahedral
0.225 - 0.414
ZnS
Octahedral
0.414 - 0.732
NaCl, TiO2
Cubic
0.732 1.0
CsCl, CaF2
2.3.1 Lattice Enthalpy (Lattice Energy) Lattice

We have seen in a qualitative manner why a sodium atom and chlorine atom might be
expected to form an ionic bond. Energy changes involved in ionic bond formation helps
to understand that why certain atoms form ionic bond and others do not. If atoms come
together and bond, there should be a decrease in energy, because a bonded state
should be more stable and therefore at a lower energy level as shown in Fig 2.4.
Figure 2.4: Potential Energy Diagram for ionic bond At a certain critical distance between
the atoms (as shown in Fig.2.4) the energy drop is maximum that results in stability. If
the distance between the atoms is decreased further it results in repulsion.
The attraction of oppositely charged ion does not stop with the bonding of pairs of ions.
The maximum attraction of ions of opposite charge with the minimum repulsion of ions
of the same charge is obtained with the formation of crystalline solid. Then even more
energy is released. Clustering of ion pairs to form an ionic solid and progressive release
of energy is shown in Fig 2.5.
Figure 2.5: Clustring of ion pairs to form ionic solid
Lattice enthalpy of an ionic compound is defined as the energy released when one mole
of the compound is formed in the regular lattice structure from requisite number of ions
(1 mole of positive ions and 1 mole of negative ions) in the gaseous state.
The lattice enthalpy of an ionic solid is also defined as the energy required for seperating
completely. one mole of a solid ionic compound into its gaseous constituent ions.
Lattice enthalpy cannot be measured experimentally. Lattice enthalpies are calculated
from experimental data using the Born-Haber cycle.
The force of attraction, , between two ions carrying unlike charges separated
by a distance, , is given by Coulombs law.Fer
The corresponding potential energy would be obtained by computing the work
done in bringing the charges to this distance from infinity.
Thus,
The negative sign indicates that this amount of energy is released by the system
resulting in lowering of potential energy, which we expect when stable bonding
has occurred.
Clustering of Ion- Pairs to form Ionic Solids

http://www.illldu.edu.in/mod/book/print.php?id=5635
2.3.2 Born-Lande Equation
Born-Lande Equation
Consider NaCl crystal having face centered cubic (FCC) structure.

Eight Na+ ions form the corners of a cube and six more are centered on the faces
of the cube.
The Cl- ions are similarly arranged so that NaCl lattice consists of two
interpenetrating FCC lattices as shown in Fig 2.6.
Figure 2.6: The crytal structural of NaCl (Rock Salt)

The quantitative evaluation of lattice energy of an ionic crystal is determined by
coulombic interactions between all of its ions (both coulombic attractions and
repulsions), Ec and repulsive forces because of the interpenetration of charge clouds, ER
.
ETotal = Ec + ER
The first theoretical interpretation of lattice enthalpy was given by Born and Lande.
They derived an equation for the calculation of lattice enthalpy of an ionic compound.
Lattice enthalpy is defined as positive;

H for this process is negative.
Where
U0 = Lattice enthalpy
r0 = Equilibrium internuclear distance
A = Madelung constant (this takes care of interaction with all other ions besides
the nearest neighbours)
NA = Avagadro constant
n = Borns exponent (it depends on the electronic configuration of the ions. Its value
may be derived either theorehically from the measurement of the compressibility of the
solid)
= Constant (3.14159)
0 = Permittivity of free space
Z+ = Charge on the positive ion
Z- = Charge on negative ion
e = Charge on an electron
For sodium chloride, the various factors are
A = 1.74756
NA = 6.022 x 1023 ions pairs per mol
Z+ = +1
Z- = -1
e = 1.60218 x 10-19 C
0 = 8.854188 x 10-12 C2 J-1 m-1
n =8
r0 = 2.814 x 10-10 m
= 3.14159
= -755.2 kJ mol-1
The Born-Lande equation gives a calculated value of lattice enthalpy, U0 = -755.2 kJ
mol-1 for sodium chloride, which is close to the experimental value of -770 kJ mol-1 at
25 C. For more precise work, several other functions have been suggested for repulsion
energy. Other variables like van der Waals forces, zero point energy and correction for
heat capacity are included. The refined value for lattice enthalpy is -757.5 kJ mol-1.
The values of lattice enthalpy calculated by means of the above equation have been
found to be in good agreement with those obtained experimentally as shown for some of
the compounds in the Table 2.2.
Table 2.2 Lattice Enthalpy of Some Compounds
Compound
Lattice Enthalpy (kJ mol-1)

Experimental
Theoretical
AgCl
-895
-849
CaF2
-2
The Madelung constant depends on the coordination number of each ion and geometric
arrangement of ions in the crystal lattice. Hence, lattice enthalpy and stability of an
ionic crystal is directly proportional to the Madelung constant. Values of Madelung
constants for different ionic crystals are given in Table 2.3.
.
Table 2.3
Madelung Constant Values for Some Common Ionic Solid
Structure
Formula
Coordination number
Sodium chloride
NaCl
Na+(6); Cl- (6)
1.7475
Cesium chloride
CsCl
Cs+ (8); Cl-(8)
1.7627
Zinc blend
ZnS
Zn2+(4); S2- (4)
1.6380
Wurzite
ZnS
Zn2+(4); S2-(4)
1.6413
Fluorite
CaF2
Ca2+ (8); F-(4)
5.0388
Example
Calculate the value of Madelung constant for MgO from the following data.
r0 = 2.10 x 10-10 m
n=7
U0 = -3940 kJ mol-1
Solution:
In case of MgO, the charges on cation and anion are +2 and -2 respectively.

Substituting the values in Born Lande equation, we have
-3940 kJ mol-1
Therefore, A = 1.74.
Factors Influencing the Magnitude of Lattice Enthalpy
The lattice enthalpy is useful in correlating properties of ionic substances because the
formation or destruction of the crystal is frequently more important step in reactions
involving ionic substances.
Some properties of ionic compounds can be explained on the basis of their lattice
enthalpy values.
The higher the charge on cation and anion, the greater would be the magnitude of the
lattice enthalpy.
-1
U0 ( kJ mol )
Na+F 914.2
Mg2+(F -)2
2882.0
<
Mg2+O23895.0
<
Smaller the size of ions, the smaller would be inter-ionic distance, the higher would be
the value of lattice enthalpy.
U0 ( kJ mol-1)
U0 ( kJ mol-1)
LiF
1034
LiF
1034
>
NaF
>
914.2
LiCl >
840.1
>
KF
812.1
LiBr
781
>
RbF > CsF

780.3
743.9
>
LiI
718
Down the group, lattice enthalpy decreases as the size of the cation increases.
U0 ( kJ mol-1)
BeO
4541
>
MgO
3895
>
CaO
3520
>
SrO >
3325
BaO
3108
The greater the lattice enthalpy, the more stable is the ionic compound.
CaCl2
(2200 kJ mol-1) > CaCl (720 kJ mol-1)
Ionic compounds with high lattice enthalpy require a greater input of thermal energy
to breakdown the crystal lattice. Consequently, the greater the strength of the ionic
solid, higher will be its melting point.
LiF
>
U0 (kJ mol-1)
1034
m.p. (C)
870
The lattice enthalpy affects the solubility of the
LiCl
>
840.1
613
ionic compounds.
LiBr
781
597
>
LiI
718
446
1. For a solid to dissolve in a solvent, the strong forces of attraction between its
ions (U0) must be overcome.
2. The solvation of ions is referred to in terms of solvation energy,which is always
exothermic.
3.
M+(g) + aq M+(aq) + hydration energy
4.
X-(g) + aq X-(aq) + hydration energy
1. These exothermic solvation energies have their origin in the electrostatic
interaction between the polar solvent molecules and the solute ions.
2. Since cations are smaller than anions, the positive field of a cation will be greater
than the negative field of an anion, so that the solvation energies of cations
generally exceed those of anions.
3. An ion with high value of the ionic potential will tend to form the solvated ion
more easily than the ion with a smaller value of ionic potential. Ionic potential is
given by
Ions with small size and high charge get extensively hydrated.
(a)
charge
Na+
(+)
Mg2+
(2+)
Al3+
(3+)
Hhydration (kJ mol-1)
422
1953
4694
(b)
size (pm)
Hhydration(kJ mol-1)
Li+ Na+ K+
Rb+
60 95 133 148
531 422 338 318
Cs+
169
280
Ionic crystals are generally soluble in polar solvents like water and insoluble in non-polar
solvent such as carbon tetrachloride. As a general rule, for a solid to dissolve in a
particular solvent, its solvation energy (Hhydration refers to hydration energy) should be
greater than the lattice energy of that solid.
solvation energy > lattice energy .. salt dissolves in the solvent
solvation energy < lattice energy .. salt does not dissolve in the solvent
Lithium chloride and lithium bromide are soluble in water since the hydration energy is
greater than lattice energy in both the cases.
LiCl
LiBr
Hhydration
883
854
U0 (kJ mol-1)
840
781
Silver chloride and Silver bromide are insoluble in water since the
hydration energy is smaller than lattice energy in both the cases.
AgCl
AgBr
Hhydration
848
815
U0 (kJ mol-1)
895
877
Some ionic compounds like sulphates and phosphates of barium and strontium are
insoluble in water inspite of being ionic. This can be attributed to the high
lattice enthalpies associated with these compounds due to polyvalent nature of
both cation and anion. In these cases, hydration of ions fails to liberate sufficient energy
to offset the lattice enthalpy.
2.3.3 The Born-Haber Cycle
Direct calculation of lattice enthalpy is quite difficult because the required data is often
not available. Therefore, lattice enthalpy is determined indirectly by the use of the Born
Haber cycle. It is based on Hesss law. Hesss law states that the enthalpy of a reaction
is the same, whether it takes place in a single step or in more than one step.
The formation of an ionic compound, MX, shown in Fig 2.7, may occur either by direct
combination of the elements or by a stepwise process involving vaporisation of
elements, conversion of the gaseous atoms into ions and the combination of the gaseous
ions to form the ionic solid.
Figure 2.7: A Schematic Representation of Born-Haber Cycle for the Formation

of Solid MX
H1 = enthalpy of atomization of the metal
H2 = enthalpy of atomization of the non-metal
H3 = ionization enthalpy
H4= electron gain enthalpy
H5 = lattice enthalpy
According to Hesss law
fH = H1+ H2+ H3+ H4+ H5
H1, H2and H3 are endothermic while H4 (first electron gain enthalpies are
exothermic and second electron gain enthalpies are endothermic) and H5 are
exothermic.
The lattice enthalpy of a solid can be calculated with the help of other thermochemical
quantities which can be measured experimentally. A schematic representation of BornHaber cycle for the formation of solid NaCl is given in Fig 2.8.
Figure 2.8: A Schematic Representation of Born-Haber Cycle for the Formation

of Solid NaCl
Let us use Born-Haber cycle for determining the enthalpy of formation of NaCl.
The standard enthalpy change, fH for the following reaction is -410.9 kJ mol-1.
Na(s) + Cl2 (g) NaCl(s)
Here, the formation of NaCl can be envisaged in five separate steps. The sum of
enthalpy changes for these steps being equal to the enthalpy change for the overall
reaction.
Na(s) + Cl2 (g) NaCl(s) fH =?
Na(s) Na(g)
Cl2 (g) Cl (g)
Na (s) Na+ (g) + e Cl2 (g) + e- Cl- (g)
Na+ (g) + Cl- (g) NaCl(s)
H1= 108.4 kJ mol-1

H2 = 120.9 kJ mol-1
H3 = 495 kJ mol-1
H4 = -355 kJ mol-1
H5 =-757.3 kJ mol-1
Applying Born-Haber cycle, we have

[fH]theoretical = +108.4 kJ mol-1 + 120.9 kJ mol-1 + 495.4 kJ mol-1
-355.5 kJ mol-1 757.3 kJ mol-1
= - 387.6 kJ mol-1
[fH]experimental = - 410.9 kJ mol-1
Close agreement between theoretical values (assuming ionic bonding) and

experimental values indicates that the assumption that bonding is ionic is infact
true.
Born-Haber cycle is mainly used for the evaluation of
Lattice enthalpies
Electron affinities
Proton affinities and
Heats of formation.
Biographic Sketch
Biographic Sketch
Example
Calculate the lattice enthalpy of KCl from the following data by the use of Born-Haber
cycle.
Enthalpy of sublimation for
K(s) K(g)
H1 = + 89 kJ mol-1
Enthalpy of dissociation for
Cl2 (g) Cl (g)

Ionization enthalpy for
K (g) K+ (g) + e-
H2= + 122 kJ mol-1

H3= + 425 kJ mol-1
Electron gain enthalpy for
Cl2 (g) +e- Cl- (g)
H4= - 355 kJ mol-1
Enthalpy of formation for

K(s) +
Cl2 (g) KCl (s)
Hf = -438 kJ mol-1
Solution:
According to Hesss law, we have
fH= H1 + H2 + H3 +H4 + H5
-438 kJ mol-1 = (+89 + 122 + 425 355) kJ mol-1 + H5
Hence, Lattice enthalpy of KCl, H5 is 719 kJ mol-1.
Example
Assuming, hypothetical NaCl2 would crystallize in the fluorite structure (A=2.52),
calculate enthalpy of formation of NaCl2. Comment on the calculated value of fH.
Enthalpy of sublimation of Na (s), H1= + 109 kJ mol-1
Enthalpy of dissociation of Cl2 (g), H2 = + 247 kJ mol-1
First ionization enthalpy of Na (g), H3I= + 494 kJ mol-1
Second ionization enthalpy of Na+ (g), H3II = + 4561 kJ mol-1
Electron gain enthalpy of Cl (g), H4= - 355 kJ mol-1
Lattice enthalpy , H5= -2155 kJ mol-1
Solution:

According to Hesss law, we have
Hf = H1 + H2 + H3 +2H4 + H5
= (+109 + 247 + 494 + 4561 - 710 2155) kJ mol-1
= +2546 kJ molSince fH is positive, NaCl2 does not exist. The extra stabilization of the lattice is
insufficient to compensate for the very large second ionization enthalpy of Na.
Summary of ionic bonding
2.3.4 Polarization and Polarizability

Anions are large in size than cations and therefore, their electron clouds are less tightly
held. When two oppositely charged ions approach each other closely, the positively
charged cation attracts the outermost electrons of the anions and repels its positively
charged nucleus. This results in the distortion or polarization of the anion.
This is illustrated in Figures 2.9 (a), (b) and (c) and 2.10. When a large and soft anion
comes under the influence of small cation, the cation is able to polarize the anion. Due
to the compact charge cloud of the cation, polarization of the cation is very small.
Figure 2.9: (a) Far apart: no influence on each other (b) Closer together: the negative
ion is
polarized by the positive ion (c) Even closer: the charge cloud
of the negative
ion merges with that of the positive ion; covalence
results
The power of an ion to distort the other ion is known as its polarizing power.
The polarizing power of a cation is proportional to its ionic potential,
The power of an ion to distort the other ion is known as its polarizing power.
The polarizing power of a cation is proportional to its ionic potential, change/ size
The large negative ion is highly polarizable.
Polarization and polarizablity

As a consequence of polarization or deformation, there occurs a transition of ionic

character to a covalent character. With increasing polarization, the charge clouds
of neighbouring cations and anions would ultimately tend to merge with one
another, as is observed in a covalent compound.
Figure 2.10: Diagram

showing the
polarization
of a
negative ion by
a
small positive ion
Fajans explained the trend of attaining covalent character by ionic compounds as a
consequence of polarization in terms of Fajans rules (1923).
In terms of the rules of Fajans
1. A small positive ion favours covalence.

2. In small ions the positive charge is concentrated over a small area. This makes
the ion highly polarizing, and very good at distorting the negative ion.
3. A large negative ion favours covalence.
4. Large ions are highly polarizable, that is easily distorted by the positive ion,
because the outermost electrons are shielded from the charge on the nucleus by
filled shells of electrons.
5. Large charges on either ion, or on both ions, favour covalence.
6. This is because a high charge increases the amount of polarization.
7. Polarization, and hence covalence, is favoured if the positive ions does not have
noble gas configuration. A noble gas configuration is most effective at shielding
the nuclear charge, so ions without the noble gas configuration will have high
charges at their surfaces, and thus be highly polarizing.
The significance of these rules is that the induced covalent character in ionic compounds
increases with decrease in size of the cation or increase in charge on the cation and an
increase in size and charge of the anion. Cations with pseudo-noble gas configuration
(18 electrons in the outer shell) exert greater polarizing power than cations with noble
gas configuration (8 electrons in the outer shell).
Biographic
For example, cations Cu+ (3s23p63d10) and Na+(2s22p6) have similar ionic radii but the
former is more polarizing and induces higher covalent character than the latter. This is
due to the additional d-electrons in Cu+ provides inadequate shielding and therefore, the
nuclear charge causes greater deformation of anion. The corresponding increase in
induced covalent character in ionic compounds is reflected in the decreasing melting

points, solubility in polar solvents and decomposition temperatures of alkaline earth
carbonates.
Effects of polarization
Melting points decrease with increasing covalent character.

NaCl (800C), CaCl2 (772C)
NaBr (747C), MgBr2 (700C), AlBr3 (97.5C)
LiF (870C), LiCl (613C), LiBr (547C), LiI (446C)
BeCl2 (405C), CaCl2 (772C)
Solubility in polar solvents decreases with increasing covalent character.
AgF, which is quite ionic, is soluble in water, but the less ionic AgI is insoluble.
Increasing covalence from fluoride to iodide is expected and decreased solubility
in water is observed likewise, KI is soluble in ethyl alcohol, whereas, KCl is
insoluble.
CuCl, AgCl are insoluble in water, whereas, NaCl is highly soluble in water.
MCO3 MO + CO2
Stability of carbonates can often be rationalized in terms of the polarizing power

of a particular cation. In the alkaline earth carbonates, for example, there is a
tendency towards decomposition with evolution of carbon dioxide.
Small size cations show greater tendency to polarize the carbonate anion (CO32-) into an
oxide (O2-) and CO2. Hence, as the size of cation increases polarizing power of the cation
decreases and the thermal stability of metal carbonates increases.
BeCO3 (unstable) < MgCO3 (350C) < CaCO3 (900C) < SrCO3 (1290C) < BaCO3
(1360C).
2.3.5 Ionic Character in Covalent Compounds and Dipole Moment
Covalent bonds having partial ionic character are referred to as polar covalent bonds.
The polarity of a bond, such as that in HF is characterized by a separation of electric
charge (partial charge, ).
+ HF
The degree of polarity in a covalent bond can be expressed in terms of the bond
moment, that is, the product of the charge, q and the internuclear distance, r, since
each bond amounts to a dipole.
=qxr
= (4.8 x 10-10 esu) (10-8 cm)
= 4.8 x 10-18 esu-cm
= 4.8 D
(1D =10-18 esu-cm)
In SI units, unit of charge is Coulombs (C) and that bond length in meters (m),
therefore has units of C m.
= (1.6022 x 10-19 C) (10-10m)
= 1.6022 x 10-29 C m
= 4.8 D
(1 D = 3.336 x 10-30 Cm)
The average polarity of a given species over a period of time is measured by its
permanent dipole moment (), which is designated as a vector, pointing from the
centre of positive charge to the centre of negative charge with a positive charge
at one end.
The permanent dipole moments of polar diatomic molecules are same as their
bond moments. The permanent dipole moments of polyatomic molecules,
however, are determined by both the bond moments and lone pair moments.
A molecule will have a dipole moment if the summation of all of the individual
bond moment vectors is nonzero.We can sometimes relate the presence or
absence of a dipole moment in molecules to its molecular geometry. For

example, consider the carbon dioxide molecule, each carbon-oxygen bond has a
polarity in which the more electronegative oxygen has a partial negative charge.
- + O=C=O
The two bond moments of equal magnitude but opposite direction cancel each other,
giving rise to a net dipole moment of zero for the molecule.
For comparison, consider water molecule. The bond moments point from the hydrogen
atoms towards the more electronegative oxygen.
Here, however, the two bond moments do not points directly towards, or away from
each other. As a result, they add together to give a nonzero dipole moments for the
molecule.
The dipole moment of H2O has been observed to be 1.85 D. If the water molecules were
linear, the dipole moment would be zero. Figs 2.11 and 2.12, and Table 2.4 give the
geometries and dipole moments of some molecules.
Biographic
Table 2.4 Dipole Moments of Some Polar Molecules
Molecule
Geometry
Dipole Moment (D)
HF
Linear
1.92
HCl
Linear
1.08
HBr
Linear
0.78
HI
Linear
0.38
H 2O
Bent
1.85
NH3
Pyramidal
1.47
SO2
Bent
1.60
Table 2.5 summarizes the relationship between the molecular geometry and dipole
moment for the molecules of type AXn in which all X atoms are identical. The geometries
in which AX bonds are directed symmetrically about the central atom (for example
linear, trigonal planar, and tetrahedral) give molecules of zero dipole moment, that is
the molecules are nonpolar. Those geometries in which the X atoms tend to be on one
side of the molecule (for example bent and trigonal pyramidal) can have nonzero dipole
moments, that is, they can give polar molecules.
Figure 2.11: Molecules with zero dipole moment
Figure 2.12: Molecules with net dipole moment
The NH3 and NF3 molecules present an interesting case in relation to the resultant dipole
moment. Although fluorine is more electronegative than nitrogen the resultant dipole
moment of NH3 (4.90 x 10-10C m) is greater than that of NF3 (0.80 x 10-30 C m) in both
cases the central nitrogen atom has a lone pair whose bond moment points away from
the nitrogen atom.
Table 2.5 Relationship Between Molecular Geometries and Dipole
Formula
Molecular Geometry
Dipole Moment
AX
Linear
Can be nonzero
AX2
Linear;
Bent
Zero;
Can be nonzero
AX3
Trigonal planar;
Trigonal pyramidal;
T-shape
Zero;
Can be nonzero;
Can be nonzero
AX4
Tetrahedral;
Square planar;
See saw
Zero;
Zero;
Can be nonzero
AX5
Trigonal bi-pyramidal;
Square pyramidal
Zero; Can be nonzero
AX6
Octahedral
Zero
In NH3 the resultant
Moment
bond moments reinforce the moment of lone pairs,
resulting into a larger net dipole moment. In NF3, the resultant of the
bond
moments (fluorine is the negative end) act in opposition to the lone pair moment, cancel
each other and hence, the net dipole moment of the NF3 molecule is lowered. Figure
2.13 shows the net dipole moments in NH3 and NF3.
Figure 2.13: Molecules with net dipole moment

Percentage of Ionic Character
The ionic character in a covalent bond may be estimated from an empirical

relationship between ionic character and electronegativity difference. Hanny and
Smith (1946) proposed a simple and the most acceptable formula for the
calculation of percentage ionic character.
Hanny and Smith formula
Percentage ionic character = 16 (A B) + 3.5 (A B)2
A and B are the electronegativities of the bonding atoms A and B.
Example
Calculate the percentage of ionic character in HCl. The experimental dipole moment of
HCl is 1.03 D and bond distance in HCl is 1.27 x 10-10 m.
Solution:
obs = 1.03 D = (1.03)( 3.34 x 10-30) C m
cal = q x r = (1.6 x 10-19 C) (1.27 x 10-10 m)
Percentage ionic character
Therefore, HCl is 17 % ionic.

There are several different theories that explain the electronic structures and describes
the shapes of different molecules
Example
The electronegativities of hydrogen and chlorine are 2.1 and 3.0. Calculate percentage
ionic character in HCl.
Solution:
Percentage ionic character = 16 (A B) + 3.5 (A B)2
= 16 (3.0-2.1) + 3.5 (3.0-2.1)2=17.2
Therefore, HCl is 17.2 % ionic.
In general, a bond corresponding to an electronegativity difference of 2.1 is nearly 50%
ionic.
The ionic character of a bond may be estimated in simple cases from its dipole
moment values Percentage ionic character =

where = Dipole moment and calculated= Distance x Charge
The study of dipole moment is very useful for information on:
polor and nonpolar character of molecules

extend of bond polarity or percentage ionic character
shapes of molecules
geometrical substitution on planar rings
2.4 Covalent Bonding

How do bonds form between atoms of the same or similar elements? How can we
describe the bonds in substances such as H2, Cl2, CO2 and literally millions of other
nonionic compounds?
The answer is that the bonds in such compounds are formed by sharing electrons
between atoms rather than by the transfer of electrons from one atom to another.
Characteristics of covalent compounds
They generally exist in gaseous or liquid phase

They have low melting point/boiling points
They are poor conductors of electricity
They are soluble in nonpolar organic solvents
Covalent compounds have definite molecular geometry.
There are several different theories, which explain the electronic structures and describe
the shapes of different molecules.
2.4.1 Lewis Theory: The Octet Rule
For many light atoms a stable arrangement is attained when the atom is surrounded by
eight electrons. A formulation of this type indicates only the importance of a shared pair
of an electron but gives no information as to how sharing is effected or as to the nature
of the bond.
Theoretical approaches and interpretations
The characteristics of covalent compounds suggest that an increase in electronic charge
density between bonded atoms occurs. This increase has been rationalized in terms of
two somewhat different theoretical approaches, each of which is the result of
approximate solutions of appropriate wave equations.
The valence-bond, or directed bond approximation, which considers covalent

interaction to occur between two atomic species as a consequence of the overlap
of two atomic orbitals of the same or nearly the same energy and proper spatial
orientation, each containing a single electron. As a result of this overlap the
charge density in the internuclear region increases and serves to hold the two
nuclei together and we say a bond is formed between atoms.
The molecular-orbital or undirected-bond approximation, which involves
delocalized molecular orbitals spread over the whole molecule. The original
atomic orbitals lose their identities.
The valence-bond approximation is modular in concept and lends itself to representation

by models or drawings depicting models, whereas the molecular-orbital approximation is
energy oriented and describes bonding in terms of energy states. Both these methods
make use of variation principle, a mathematical technique used to calculate the ground
state energy of a system.
2.4.2 Heitler-London Theory (Valence Bond Approach)

The formation of a chemical bond of any type is possible only if the approach of the
atoms towards one another is accompanied by decrease in energy.
According to valence bond theory, covalent bond may be seen as accumulation of high
charge density in the internuclear region resulting from the overlapping of atomic
orbitals. The strength of the bond depends on the extent of the overlapping-- greater
the overlapping stronger the bond.
Consider the formation of the covalent bond between two hydrogen atoms to give the H2
molecule. As the atoms approach one another, their 1s orbitals begin to overlap. Each
electron can then occupy the space around both atoms. In other words, the two
electrons can be shared by the atoms. The electrons are attracted simultaneously by
the positive charges of the two hydrogen nuclei. This attraction that bonds the electrons
to both nuclei is the force holding the atoms together.
It is interesting to see how the potential energy of the atoms changes as they approach
and then bond. Fig 2.14 shows the potential energy of the atoms for various distances
between the nuclei. As the atoms approach (moving from right to left on the potential
energy curve), the potential energy gets lower and lower. This continues till a certain
distance called as the bond length and on further decreasing the distance between the
two atoms, the repulsive forces become predominant and the energy increases.
Figure 2.14: The potential energy curve for the formation of H2 molecule as a function
of
internuclear distance
Now imagining the process to be reversed, energy must be added to seperate the atoms
in the molecule from their normal bond length to infinite distance. This energy that must
be added is called the bond dissociation energy. Higher the bond dissociation energy,
the stronger would be the bond.]
In the case of hydrogen molecule, the distance between the two hydrogen atoms
corresponding to minimum energy is 74 pm and the decrease in potential energy in the
formation of H2 molecule has been found to be 431.4 kJ mol-1. Therefore, H2 molecule
would be much more stable than hydrogen atoms due to decrease of energy.
Heitler-London
proposed
quantum-mechanical
treatment
of
the
hydrogen
molecule. According to this theory, the calculated bond distance is 74.9 pm and the
decrease in potential energy is 388 kJ mol-1. Introduction of sufficient parameters can
improve the wave function to any desired accuracy, giving rise to the bond distance 74
pm and potential energy 431.4 kJ mol-1.
By making use of the concept of hybridization, VB theory, succeeds in accounting for the
principles of molecular geometry. By introducing the idea of resonance, it rationalizes
the chemical properties of many molecules.
Biographic
Types of Overlapping of Atomic Orbitals and Orbital Diagrams

Different types of overlapping which we come across are
i.
ii.
iii.
iv.
v.
vi.
vii.
overlappings-s
s-p overlapping
pz-pz overlapping
px-px overlapping
py-py overlapping
p-d overlapping
d-d overlapping, etc.
A sigma bond () is formed by the overlap of atomic orbitals along the internuclear axis
while a pi bond is formed by the lateral (sideways) overlap of atomic orbitals. Sigma
bond is a stronger bond because the extent of overlap is quite large. Pi bond is a weaker
bond because the extent of overlapping is small.
Hydrogen fluoride molecule forms through s-p overlap. The half filled 2pz orbital of
fluorine overlapps with half filled 1s orbital of hydrogen atom resulting in the formation
of sigma bond. The formation of sigma bond in hydrogen fluoride molecule is shown in
Fig 2.15.
Figure 2.15: Formation of a sigma bond

Formation of a pi bond occurs if a sigma bond is already present i.e., it cannot be
present alone. Formation of pi bond is illustrated in the formation of a nitrogen
molecule. Electronic configuration of nitrogen is 2s22px12py12pz1. Thus there are three p
orbitals having unpaired electrons, the 2pz orbital of one nitrogen atom overlaps with 2pz
orbital of the other nitrogen atom forming a sigma bond. The 2px1 and 2py1 of one
nitrogen atom overlap with 2px1 and 2py1 of the other nitrogen atom laterally to form
two pi bonds. Thus nitrogen atom has one sigma bond and two pi bonds i.e., a triple
bond. The formation of one sigma bond and two pi bonds in nitrogen molecule are
shown in Fig 2.16.
Figure 2.16: Formation of N2 molecule

Although a simple orbital overlapping concept is able to describe the formation of bonds
in simple molecules but fails in the case of molecules like BeF2, BF3, CH4, PF5, SF6, etc.
Let us discuss the linear geometry of BeF2. The electronic configuration of beryllium
(Z=4) is 1s22s2.
According to the atomic orbital overlap concept, beryllium should behave like noble gas
since it has no half filled orbital. But beryllium forms a number of compounds like BeF2
and BeH2 in which it is bivalent. In order to explain these anomalies and describe the
geometries of covalent molecules, we make use of new concept called hybridization.

2.4.3 Concept of Hybridization
Linus Pauling in 1931 introduced the idea of hybrid orbitals.
Hybridization is the mixing of atomic orbitals in an atom (usually a central atom) to
generate a set of new atomic orbitals called hybrid orbitals. Hybrid orbitals are used to
form covalent bonds.
Hybridization is a concept and takes place in chemist calculations not in actual
molecules. We accept hybridization not because of its objective reality but because it
gives results that are consistent with our knowledge of molecular bonding and molecular
geometry.
Biographic
Rules of hybridization
Hybridization is a process of mixing of orbitals on a single atom (or ion).

Hybridization is not a predictive tool but simply reproduces observed shapes;
they describe not explain experimental facts.
Only orbitals of similar energies can be mixed to form good hybrid orbitals.
The number of orbitals mixed together always equals the number of hybrids
obtained.
In hybridization, we mix a certain number of orbitals, not a number of
electrons. The electrons are arranged in the hybrid orbitals.
Most hybrids are similar, but they are not necessarily identical in shape; they
differ from one another largely in orientation in space.
Since s orbitals are directionless in xyz space, they add no direction when
contributing to hybrids. They add plumpness only.
Other orbitals with pronounced direction in space (p, d, etc) determine the
directional properties of hybrids.
The particular type of hybrid chosen for a structure discussion is determined by
the experimentally known geometry of the molecule i.e., observe bend angles of
120 should hint of sp2 hybrids, linear systems of sp hybrids, and tetrahedral
shapes or 109 bond angles of sp3 hybrids.
The concept of hybridization is described in the following examples. The linear geometry
of BeF2 can be described by assuming Be to be sp hybridized. The two sp hybrid orbitals
overlap with the two 2pz orbitals of fluorine to form two covalent bonds.
The electronic configuration of Be atom in its ground state is 1s22s2. The promotion of 2s
electron to 2p orbital results in an excited state configuration of Be, i.e; 1s22s12pz1. It is
then postulated that the s and p orbitals of Be mixed with each other i.e., hybridised to
give identical orbitals i.e., (orbitals of equivalent energy)(Figure 2.17, 2.18 and 2.19).
Figure 2.17: sp hybridization for Be
Figure 2.18: Shape of a sp hybrid orbital
Figure 2.19: Formation of two sp hybrid orbitals by mixing s and p orbitals
Figure 2.20: Linear beryllium fluoride molecule resulting from overlapping of sp

hybrid
orbitals of Be and 2pz orbital of fluorine atom.
Since in the formation of bivalent compounds of beryllium one s and one p orbital is
involved in hybridization, it is called sp hybridization and the resulting orbitals are called
hybrid orbitals. The electronic configuration of fluorine is 2s22px2 py2 pz1. The half filled pz
orbital of each fluorine atom overlaps with each of the two half filled sp hybrid orbitals of
beryllium to form two covalent bonds (Figure 2.20).
Thus, with the help of concept of hybridization, we are successful in describing the
bonding as well as the geometry in BeF2 molecule.
.The quantum mechanical wave functions for s and p atomic orbitals derived from
Schrodinger wave equation can be mathematically combined to form a new set of
equivalent wave functions called hybrid atomic orbitals
For sp hybridization, we have the following equations.
sp1 =
N (s +p)
sp2 =
N (s - p)
is the normalizing coefficient and sp1 and sp2 are the new diagonal or sp
hybrid orbitals.
Energetics of Hybridization
As an illustration, we may consider the formation of methane molecule. The outer
electronic configuration of carbon atom in the ground state is 2s2p2. Energy is required
for the promotion of an electron 2s to 2p.
Figure 2.20: Linear beryllium fluoride molecule resulting from overlapping of sp

hybrid orbitals of Be and 2pz orbital of fluorine atom.
Energy is released in the formation of covalent bonds involving sp3 hybrid orbitals.
Formation of hybrid orbitals of equivalent energy is shown in Fig. 2.21
Figure 2.21: Formation of hybrid orbitals of equivalent energy
Figure 2.22: Formation of four sp3 hybrid orbitals by overlapping of one s and
three p orbitals
The energy of the resulting hybrids is the weighted average of the participating atomic
orbitals.
Esp3 =
[Es + 3EP]
=
= -1241 kJ mol-1
sp3d Hybridization
Non metal atoms like phosphorus (3s23p33d) can exhibit variable covalency due to
availability of vacant 3d orbitals. The possibility of sp3d hybridization in phosphorus
describes the formation and trigonal bipyramidal (TBP) geometry of PF5 molecule (Fig
2.23) and for PCl5 molecule (Fig 2.24).
Figure 2.23: TBP geometry of PF5 molecule resulting from sp3d hybridization of
valence Shell orbitals of central P atom
sp3d hybrid orbitals are directed towards the corners of a trigonal bipyramid. They form
three coplanar bonds with bond angles of 120 and two bonds at right angles to this
plane, one above and one below.
Figure 2.24: Trigonal bipyramidal geometry of PCl5
sp3d2 or d2sp3 Hybridization
Sulphur hexafluoride (SF6) provides an example of sp3d2 hybridization.

Combination of one s, three p, and two d orbitals leads to six hybrid orbitals which are
directed towards the corners of regular octahedron (Fig 2.25).
Figure 2.25: Octahedral geometry

for SF6 involving sp3d2 hybridization
Hybridization in Molecules Montaining Multiple Bonds

Let us consider the geometry of carbon dioxide, CO2 .
The electronic configuration of carbon in ground state is 2s2 2px1 2py1 and in the excited
state is 2s1 2px1 2py1 2pz1. The outer electronic configuration of oxygen atom in ground
state is 2s2 2px2 2py1 2pz1.

In the formation of CO2 molecule, hybridization of orbitals of carbon occurs only to a
limited extent i.e.; sp hybridization is assumed. The two sp-orbitals of carbon overlap
with 2pz orbitals of each oxygen atom to form two -bonds. The carbon atom is still left
with two unpaired 2p electrons whose axes are perpendicular to each other and to the
internuclear axes. These unhybridized orbitals of carbon (p orbitals) engage in the
formation of bonds with p orbitals of oxygen atom by the lateral overlap of these
orbitals (Figs 2.26 and 2.27).
Figure 2.26: Linear geometry of CO2 molecule resulting from sp hybridization of

carbon atom
Figure 2.27: Formation of CO2 molecule by the overlapping of sp hybrid

orbitals of carbon and two pz orbitals of two oxygen atoms as well as p- p
overlapping.
We have seen that hybridization is a useful theoretical concept, as it helps us in
describing many structural features of molecules. Hybrid orbitals and their geometries
are shown in Fig 2.28 and summarized in Table 2.6.
Table 2.6 Hybrid Orbitals and Their Geometry
Hybridization
Number of Hybrid
Orbitals
Shape of
Molecule
Example
sp
Linear
BeCl2
sp2
Triangular planar
BCl3
sp3
Tetrahedral
CH4
dsp2
Square planar
[PtCl4]2-
sp3d
Trigonal
bipyramid
PCl5
sp3d2
Octahedral
SF6
2.4.4 Valence Shell Electron Pair Repulsion Theory (VSEPR)

VSEPR theory was originally proposed by Sidgwick and Powel in 1940 and further
developed and refined by Gillespie and Nyholm in 1957. VSEPR theory is a simple
treatment for understanding the shapes of molecules. It is not exactly a model for
explaining the formation of the bond or chemical bonding. It is an approach that can be

visualized as an extension of the simple concept of shared electron pair to rationalise
and predict the geometry of a molecule that compares favourably with those determined
experimentally (X-ray diffraction, neutron diffraction etc.)
Figure 2.28: Hybrid orbitals and their geometry
The stereochemistry of the central atom in a molecule is determined by the

repulsive interactions among all the electron pairs (eps) in its valence shells. The
electron pairs may be bonded (bps) or lone pairs (lps) pairs.
The number of electron pairs is half of the summation of electrons present in the
valence shell of the central atom and the electrons contributed by the combining
atoms.
Thus, in the case of CH4, NH3 and OH2 molecules, the number of electron pairs
present around the central atom would be
,
,
.
However, the number of bps are 4, 3 and 2 and lone pairs are 0, 1, and 2
respectively.
Electron pairs tend to minimize repulsions. If the central atom is surrounded by
only bond pairs, then the repulsions among bps are equal and the molecule
would have a regular geometry. On the other hand, when the central atom is
surrounded by both bps as well as lps, then the repulsions among them are
unequal, which is of the order: lone pair - lone pair > lone pair - bond pair >
bond pair - bond pair and the molecule would have a distorted or irregular
geometry.
Accordingly, the presence of one or more orbitals with lone pairs of electrons has
the effect of altering the bond angles i.e., the molecules with lps of electrons do
not retain regular geometry.
For the prediction of geometrical shapes of molecules with the help of VSEPR model, it is
convenient to divide molecules into two categories
1. molecules in which the central atom has no lone pairs, i.e., surrounded by only
bond pairs and
2. molecules in which the central atom has one or more lone pairs, i.e., surrounded
by both bond pairs as well as lone pairs.
Tables 2.7 shows the arrangement of electron pairs about a central atom (A) and X
represents the surrounding atom.
Table 2.7
Geometric arrangements of electron pairs around central atom
Molecule
Number of electron
pairs
Number of
bond pairs
Regular geometry
Example
AX2
Linear
BeCl2
AX3
Planar Trigonal
BF3
AX4
Tetrahedral
CH4
AX5
Trigonal bipyramidal
PCl5
AX6
Octahedral
SF6
Let us take an example wherein we take different systems containing four electron pairs
with different combinations of lone pairs and bond pairs and observe their shape and
bond angles.
In CH4 molecule, all of the valance-shell electron pairs about the carbon atom are
bonding and because all of the bonds are alike, we expect the CH4 molecule to have an
exact tetrahedral geometry with bond angle 109.50. However, if one or more of the
electron pairs is non bonding or if there are dissimilar bonds, all four valence-shell
electron pairs will not be alike. Then we expect the bond angles to deviate from 109.50
and geometry becomes distorted.
.
Table 2.8
Molecule
Molecular geometries of molecules with four electron pairs with different

combinations of lone pairs and bond pairs resulting into irregular
geometry.
Number of
Number of
Molecular geometry
Bond angles
bond pairs
lone pairs
CH4
Tetrahedral
109.5
NH3
Trigonal pyramidal
107
OH2
Angular
104.5
Figure
2.29:
Molecular geometries of molecules with 4 electron pairs with

different combinations of lone pairs and bond pairs resulting
into irregular geometry.
Consider the trigonal pyramidal molecule, NH3. The lone pair on the nitrogen atom
requires more space than the bonding pairs. Therefore, the N-H bonds are effectively
pushed away from the lone pair, and the H-N-H bond angles become smaller than the
tetrahedral value of 109.5. Consequently, NH3 molecule has distorted tetrahedral or
trigonal pyramidal geometry with a bond angle 107. Similarly H2O molecule with two
lone pairs has bent geometry with a bond angle 104 (Table 2.8 and Fig 2.29).
Central atom with five or six valence-shell electron pairs
Five electron pairs tend to have a trigonal bi-pyramidal (TBP) arrangement and six
electron pairs tend to have an octahedral arrangement. In trigonal bi-pyramidal

geometry, the vertexes are not all equivalent (that is, the angles between the electron
pairs are not all the same). Thus, the directions to which the electron pairs are directed
are not equivalent. Two of the directions, called axial directions, form an axis through
the central atom. The other three directions are called equatorial directions. The
equatorial orbitals point towards the corners of the equilateral triangle that lies on a
plane through the central atom, perpendicular (at 90) to the axial directions. The
equatorial directions are 120 from each other.
When one or more of the five electron pairs are lone pairs, the TBP geometry gets
distorted. Consider the SF4, ClF3 and XeF2 molecules with one, two and three lone pairs
on the central atoms respectively. Lone pairs in TBP geometry always occupy equatorial
positions to minimise repulsions. Accordingly, sulphur tetrafluoride has see-saw
geometry, chlorine trifluoride has T-shaped geometry and xenon difluoride has linear
molecular geometry.
In case of sulphur tetraflouride, the central atom is surrounded by five sp3d hybrid
orbitals. One of these contains a lone pair of electrons while the other four contain one
unpaired electrons each of which ovrlap with p orbitals of fluorine atoms to form four S-F
bonds. According to VSEPR theory, such a molecule with five electron pairs and
repulsions among them should have a trigonal bipyramidal geometry with bond angles
of 90 and 120. However, due to the presence of a lone pair of electrons, there is a
distortion in the geometry of SF4 molecule resulting in see-saw geometry (Fig 2.30).
Figure 2.30: Structure (see-saw) of

SF4 Molecule in which one pair (lps) of electrons occupy equatorial position
It may be noted that lone pair present in SF4 molecule can either occupy an equatorial
position or an axial position as shown below in Fig. 2.31. Considering the postulate of
VSEPR theory, that repulsions between electron pairs at angles greater than 115 apart
are neglected, we will be able to assign the most stable geometry of SF4 molecule.
Figure 2.31: Possible geometries of SF4 molecule
Figure 2.32:Structure (T-shaped) of ClF3 molecule in which two lone pairs (lps)
occupy equatorial positions
As a rule, if lone-pair occurs in a trigonal bi-pyramidal geometry, the lp always occupies
equatorial position to minimize the repulsions. Consequently, the molecule will have
distorted trigonal bi pyramidal geometry.
Similar arguments indicate that ClF3 will have T-shaped geometry (Fig 2.32).
In sulphur hexafluoride, there are six electron pairs (all bonding pairs) around sulphur
atom. Thus, it has an octahedral molecular geometry, with sulphur at the centre of the
vertexes. In iodine pentachloride, IF5 (five bond pairs and one lone pair) the lone pair of
iodine occupies one of the six equivalent positions in the octrahedral arrangement,
giving a square pyramidal geometry. In xenon tertafluoride, XeF4 (four bond pairs, two
lone pairs), the two lone pairs on xenon occupy opposite positions in the tetrahedral
arrangement to minimize their repulsion. The result is a square planar geometry.
Molecular geometries of molecules with a total of five and six electron pairs with
different combination of lone pairs and bond pairs are summarized in Table 2.9.
Table 2.9
Table 2.9 Molecular Geometries of Molecules with a total of five and

six electron pairs with different combinations of lone pairs and
bond Pairs.
No. of electron pairs
Shape
Examples
Total
Bond pairs
Lone pairs
5
5
0
trigonal bi-pyramidal
PCl5, SnCl55
4
1
see - saw
TeCl4, SF4
5
3
2
T - shaped
ClF3, BrF3
5
2
3
linear
XeF2, ICl26
6
0
octahedral
SF6, PF66
5
1
square pyramidal
IF5
6
4
2
square planar
BrF4-, XeF4
Limitations of VSEPR Theory
It fails for most of the 14 electron systems.

The geometry of alkaline earth halides (vapour) is V-shaped, although there are
no lone pairs on the central atom.
Lone pairs in some cases are stereochemically active and in some cases
stereochemically inactive.
2.4.5 Hybridization and VSEPR Theory Together

The best way to describe the geometry of covalent molecule/ion is by combining both
hybridization and VSEPR theory. Table 2.10 shows the geometries of some molecules in
which the central atom is surrounded by only bond pairs (bps) of electrons.
As already mentioned, the presence of one or more orbitals, containing lone pairs in the
valance shell and the participation of unshared electron pairs (lps) in the hybridization
scheme, causes the distortion in the regular geometry (Table 2.11 and Figures 2.33,
2.34, 2.35, 2.36, 2.37 and 2.38).

Table 2.10 Geometry of Covalent molecules involving different
types
of Hybrid orbitals of the central atom
Molecule Type of Hybridization
Number of
Geometry of the
Bond
Involved
Electron Pairs (All
Molecule
Angles
Bond Pairs)
BeF2
sp
2
Linear
180
2
BF3
sp
3
Trigonal planar
120
3
CH4
sp
4
Tetrahedral
109.5
PCl5
5
Trigonal bi
120and 90
sp3d
pyramidal
3 2
SF6
sp d
6
Octahedral
90
3 3
IF7
sp d
7
Pentagonal bi- 72 and 90
pyramidal
Table 2.11 Geometry of covalent molecules involving different
types of
hybrid orbitals, lone pairs and bond pairs on
the central atom
Number of Valence Shell
Electron Pairs on a
Hybridization and
Central Atom
Example
Type of
Shape of
Distribution of
Molecule
Molecule
Orbitals
Bond
Lone Pair Total
Pair
AX2
AX2L
2
2
0
1
2
3
sp
sp2
Linear
Trigonal
planar
Linear
Bent (V shaped)
AX2L2
sp3
Tetrahedral
Bent (V shaped)
AX2L3
sp3d
Linear
AX3
sp2
trigonal
planar
triangular
AX3L
sp3
Tetrahedral
Trigonal
pyramidal
AX3L2
sp3d
T - shaped
AX4
sp3
Tetrahedral
Tetrahedral
AX4L
sp3d
See-Saw
AX4L2
sp3d2
Octahedral
Square
planar
AX5
sp3d
Cl-Be-Cl
AX5L
sp3d2
Octahedral
Square
pyramidal
AX6
sp3d2
Octahedral
Octahedral
Geometry of molecules involving sp3 hybridization

Water molecule is formed with sp3 hybridization involving two bond pairs and two lone
pairs (Figure 2.33).
Figure 2.33: Angular geometry of H2O molecule resulting from sp3 hybridization.
Geometry of molecules involving sp3d hybridization
The molecules involving sp3d hybridization are
1. SF molecule (Figure 2.34)4
2. ClF3 molecule (Figure 2.35)
3. XeF2 molecule (Figure 2.36)
Figure 2.34: Distorted 4-coordinate geometry of SF4 molecule resulting from

sp3d
hybridization.
Figure 2.35: Distorted T-shaped geometry of ClF3 molecule involving sp3d hybridization
Figure 2.36: Linear geometry of XeF2 molecule involving sp3d hybridization.
Geometry of molecules involving sp3d2hybridization

Molecules IF5 (five bond pairs and one lone pair) and XeF4 (four bond pairs and two lone
pairs) involve sp3d2 hybridization (Figure 2.37 and Figure 2.38).
Figure 2.37: Square pyramidal geometry of IF5 involving sp3d2 hybridization
Figure 2.38: Square planar geometry of XeF4 involving sp3d2 hybridization

The geometries of molecules described by a generic formula AXmLn, are shown in Fig
2.39, where A is the central atom, X is any atom or group of atoms surrounding the
central atom, and L represents a lone pair of electrons.
Hybridization and VSEPR Theory Together

Figure 2.39: Regular and distorted geometries of some covalent molecules
Geometry of some ions

The number of sigma bonds involved in bonding of atoms and the number of lone pairs
of electrons present around the central atom determines the geometry of the
ion. Electrons involved in multiple bond formation do not take part in the hybridization
scheme. The pi bonds are excluded from hybridization. X-ray crystallography has
indicated that NO3- ion (Fig 2.40) and CO32- ion have trigonal planar geometry; SO42- ion
(Fig 2.40) and ClO4- ion have tetrahedral geometry and ClO3- ion has pyramidal
geometry.
Figure 2.40: Geometries of NO3- and SO42- ions as indicated by X-ray

crystallography
Let us describe geometries of different ions with the help of hybridization concept.
Geometry of the nitrate ion
The outer electronic configuration of nitrogen atom 2s22p3 and oxygen atom is 2s22p4.
Since the nitrate ion carries a unit negative charge, one of the oxygen atoms carries one
extra electron, i.e., it becomes O- ion. The three orbitals (one 2s and two 2p) of the
nitrogen atom hybridize to give three sp2 hybrid orbitals.
Figure 2.41: Trigonal planar geometry of nitrate ion involving sp2 hybridization
of the
central atom
Geometry of sulphate ion
The ground state electronic configuration of S atom is 3s23px2py1pz1 and the excited state
electronic configuration is 3s13px1py1pz1dxy1dyz1. One 3s and three 3p orbitals hybridize to
produce four sp3 hybrid orbitals, involving four sigma bonds. The d orbitals are excluded
from hybridization and they involve in the formation of pi bonds.
Figure 2.42: Tetrahedral geometry of sulphate ion involving sp3 hybridization of

the central
atom
The sulphate ion carries two units of negative charge. Therefore, two of the oxygen
atoms may be considered to have one additional electron each forming O- ion. This is a
case of sp3 hybridization involving four sigma bonds. The SO42- ion has tetrahedral
geometry (Figure 2.42).
Geometry of chlorate ion
The ground state configuration of chlorine atom is 3s23px2py2pz1 and the second excited
state is 3s23px1py1pz1dxy1dyz1. One 3s and three 3p orbitals of the chlorine atom hybridize
to give four sp3 hybrid orbitals. Chlorine atom forms three sigma bonds with three
oxygen atoms and also two pi bonds by lateral overlapping of 3d orbitals.
Figure 2.43: Geometry of ClO3The geometry of ClO3- ion is actually pyramidal. This is due to the fact that a lone pair of
electrons occupies one of the sp3 hybrid orbitals. The repulsions between lone pair-bond

pair electrons results in the distortion of the tetrahedral geometry leading to pyramidal
geometry (Figure 2.43).
The geometry of ClO4- ion, on the other hand, is tetrahedral. In the excited state of
chlorine atom, three electrons (two from p orbitals and one from s orbital) get excited to
give the configuration 3s13px1py1pz1dxy1dyz1dxz1. One 3s and three 3p orbitals of the
chlorine atom hybridize to give four sp3 hybrid orbitals. These orbitals contain one
electron each and are used in the formation of four bonds with four oxygen atoms. The
three electrons from 3d orbitals are used for the bond formation with three oxygen
atoms (Figure 2.44).
Figure 2.44: Geometry of of ClO42.4.6 Bond Angles

Bond angles in covalent molecules / ions are influenced by various factors such as
i.
Electrons on the central atom.

CO has no lone pair; bp-bp repulsion places the
bond at 180. In SO, repulsion of the bond pairs by the lone pairs on S makes the
molecule
SO
bent
NO > NO > NO
180
132
115
Decreasing
bond angle is due to the increasing number of electrons on the central nitrogen
atom, from zero on NO to one in NO and two in NO. The repulsion caused by a
lone pair of electrons is greater than that due to a lone electron.
2 22
+ 2 22
ii.
+ 2 22
Electronegativity of the central atom

The bond angle decreases with decrease in electronegativity of the central atom.
NH3 > PH3 > AsH3 > SbH3
107
94
92
91.3
H2O > H2S > H2Se > H2Te
104.5 92.6
91
90.5
More electronegative central atom draws the bond pairs towards itself and
repulsions among bond pairs increase and hence bond angle increases.
iii.
Electronegativity of substituents (surrounding atoms)

The bond angle increases with the decrease in electronegativity of the
surrounding atoms.
PF3 < PCl3 <PBr3 < PI3
97 100 101
102
OH2
> OF2
NH3
107
>
104.5
103.2
NF3
102
iv.
As the electronegativity of the surrounding atoms increases, the bond pair is

drawn away from the central atom, repulsions among bond pairs decrease and
hence bond angle decreases.
Molecules involving multiple bonding
PH3 <
PF3
94
98
The increase in bond angle is attributed to the enhanced repulsion due to the
presence of double bond in PF3. Due to multiple bond, the bp-bp repulsions
increase to give a higher bond angle.
v.
2.4.7 Concept of Resonance and Resonance Energy

Some covalent compounds cannot be assigned one single structure to explain all their
properties. A number of closely resembling structures are drawn, which in a combined
way explain all their properties. These closely resembling structures are known as
resonating structures and the phenomenon is known as resonance.
By giving the central oxygen an octet in ozone, the possible Lewis structures are:
II
Which of the above possible structures for O3 is correct?

Infact, neither is correct by itself. Structural studies show that OO bonds are
indistinguishable. The actual electronic structure is an average of the different
possibilities, called a resonance hybrid (fig 2.45).
Figure 2.45: Resonance in Ozone Molecule. I and II Represent the Canonical

Forms.
Various resonating structures for NO3- ion are given in Fig 2.46.
The electron pair, which forms a double bond wherever written is not localized in
any one of the two bonds, but rather smeared out over all the bonds.
The various structures of which the ions/molecules is said to be a resonance
hybrid are known as contributing structures or canonical forms or mesomeric
structures. They cannot be isolated, i.e., the canonical forms have no real
existence.
Figure 2.46: Resonance in NO3- ion I , II and III represents the canonical forms.
A straight, double- headed arrow always indicates resonance; it is never used any other
purpose
There are certain rules to write various canonical forms which contribute towards
resonance.
The contributing structures should have the same relative arrangement of atoms.
They should differ only in the positions of electrons.
The contributing structure should have the same number of unpaired electrons.
The contributing structures should be of comparable energy.
The contributing structures should be such that the negative charge resides on an
electronegative element and positive charge resides on an electropositive
element.
In contributing structure, like charges should not reside on atoms close to each
other and unlike charges should not be widely separated.
The larger the total number of covalent bonds, the more important is the
contributing structure.
Misconceptions
Benzene does not contain equal properties of molecules with structures shown in Fig
2.47, nor is there a tautomeric equilibrium nor can it be said that benzene exists for a
certain fraction of time in the form (I) and for another fraction of time as (II).
The molecule itself has a single structure of its own which cannot be described
directly by a conventional bond diagram.
Figure 2.47: Resonance in benzene molecule

Analogy
Compare the true structure with a mule which is described in terms of two other
animals a donkey and a horse. Thus the mule is an animal in its own right but it has
the characteristics of both a horse and a donkey, however, it is not either of these.
Characteristic of Resonance (Experimental Evidence)

Measured internuclear distances do not always conform to summations of
appropriate single, double, and triple bond radii. They have intermediate values.
Different canonical forms for CO2 molecule are given in Fig 2.48.
Figure 2.48: Resonance in CO2 molecule

The calculated bond length between two oxygen atoms (O-O) is 244 pm and that
observed is 230 pm. The observed bond length is smaller than the calculated bond
length of any canonical forms.
Stability of a molecule in question is more (by resonance energy) than that
predicted by any contributing molecular structure (Fig 2.49) .
The resonance energy can be evaluated as the difference between observed

enthalpy of formation and that calculated for the most stable canonical structure.
Figure 2.49: Resonance energy for the structures I, II and III of CO2
For example, the enthalpy of formation of benzene fH calculated from its enthalpy of
combustion and the enthalpies of formation of its products is -5535 kJ mol-1, whereas
the value calculated from the summation of bond energies, 6 CH + 3 CC + 3 C=C
bonds, is 5381 kJ mol-1. The benzene molecule is thus more stable by 154 kJ mol-1 due
to resonance. Similarly, for CO2, the resonance energy is 138 kJ mol-1.
E = Resonance Energy
= Eactual Emost stable canonical structure
= Eobserved Ecalculated
= -1602.5 kJ mol-1 - 2[Energy of C=O bond]
= -1602.5 kJ mol-1 + 1464.5 kJ mol-1
= -138.0 kJ mol-1
The dipole moment of a molecular species is less than that predicted in terms of
contributing structures.
The chemical properties of a given species are not those of a specific canonical
form but rather those of a hybrid of all forms.
2.4.8 Limitations of Valence Bond Treatment

B theory accounts for the stability of the covalent bond in terms of an overlap of atomic
orbitals, it explains structural features of molecules and polyatomic ions. Hybridization
and resonance concepts are useful in describing the geometry and chemical properties
of many molecules and ions. However, VB theory has certain limitations.
It assumes that the electrons in a molecule occupy atomic orbitals of the

individual atoms.
It fails to explain the bonding in electron deficient compounds, metals and

intermetallic compounds.
VB model is unable to predict correctly the magnetic properties of many
molecules e.g., O2, B2 are paramagnetic and C2 diamagnetic etc.
2.4.9 Molecular Orbital Method (Undirected Bond Approach)

The molecular orbital (MO) theory is the second approach to bonding in molecules.
The basic principles of molecular orbital theory are as follows:
MO theory describes covalent bonds in terms of molecular orbitals, which result

from merging of the atomic orbitals of the bonding atoms.
The molecular orbital is associated with all of the atomic species involved and is
polycentric while an electron in an atomic orbital is influenced by one positive
nucleus only (monocentric).
Each molecular orbital is described by a wave function , known as molecular
orbital wave function.
The molecular orbital wave function is such that the value of 2 at a point
represents the probability of finding the electron at that point provided the wave
function is a normalized wave function.
The wave function describing a molecular orbital may be obtained by Linear
Combination of Atomic Orbitals (LCAO).
Linear Combination of Atomic Orbitals (LCAO)

According to this approach the atomic orbitals (on different atoms) of comparable
energies and of appropriate symmetry combine (merge) to give rise to an equal number
of molecular orbitals. Atomic orbitals of constituent atoms combine in a linear (additive)
fashion to form molecular orbitals.
Linear Combination of Atomic Orbitals (LCAO)
According to this approach the atomic orbitals (on different atoms) of comparable
energies and of appropriate symmetry combine (merge) to give rise to an equal number
of molecular orbitals. Atomic orbitals of constituent atoms combine in a linear (additive)
fashion to form molecular orbitals.
Consider two atoms A and B each possessing a single valence electron. Let A and B
represent the wave function (amplitude) of atoms A and B respectively.
Wave functions which have the same sign may be regarded as waves that are in phase,
which when combined add up to give a larger resultant wave. Similarly wave functions
of different signs correspond to waves that are completely out of phase and which cancel
each other by destructive interference.
Atomic orbitals A and B combine to give molecular orbitals, bonding (b) and
antibonding (a).
Case (i)
When the two waves are in phase, they add up and the amplitude of the new wave is
bonding molecular orbital.
b = A + B
Case (ii)
When the two waves are out of phase, the waves are subtracted from each other so that
amplitude of the new wave is antibonding molecular orbital.
a = A - B
Knowing that the probability is given by square of the amplitude
b2 = A2 + B2 + 2AB
a2 = A2 + B2 - 2AB
AB dv is known as overlap integral, S, where dv is a small volume element. S is a

measure of the bond strength in the resulting molecular species.

If S = 0, there is no overlap, no bonding (the orbitals are non-bonding)
If S > 0, there is bonding interaction (the orbitals are bonding)
If S < 0, there is opposition to bonding (the orbitals are antibonding)
Pictorial representation of combination of atomic orbitals to form molecular orbitals is
shown in Figs 2.50, 2.51 and 2.52. The differences between bonding molecular orbitals
and antibonding molecular orbitals are given in Table 2.12.
Figure 2.50: Formation of molecular orbitals from two 1s atomic orbitals
Figure 2.51: Combination of pz orbitals (sigma bond) and combination of px and

py orbitals (pi bond)
Nonbonding molecular orbitals

The combining orbitals must have similar symmetries along internuclear axis. No
molecular orbital can result inspite of the overlap of the px or py orbital with s orbital of
two different atoms. In fact, ++ overlap is cancelled by + - overlap (Figure 2.52).
Figure 2.52: Formation of non-bonding molecular orbitals from 2s and 2 px

orbitals

Table 2.12 Differences between bonding molecular orbitals
and
anti bonding molecular orbitals
Bonding molecular orbital (BMO)
Antibonding molecular orbital

(ABMO)
1. ABMO is formed by the addition An ABMO is formed by the subtraction

overlap of atomic orbitals. = +
overlap of atomic orbitals
a A B
a = A - B
2. It has lower energy than the atomic It has higher energy than the atomic
orbitals from which it is formed.
orbitals from which it is formed.
3. The electron charge density in between
the nuclei is high and hence the
repulsion between the nuclei is very
low. This results in stabilization of the
BMO.
The electron charge density in between

the nuclei is low and hence the
repulsion
between
the
nuclei
is
high. This results in de-stabilization of
ABMO.
Stability of molecules in terms of bonding and antibonding electrons

The energy of the bonding molecular orbital is lower than that of the atomic orbital by
an amount , stabilization energy. Similarly, the energy of the antibonding molecular
orbital is increased by ', destabilization energy (Fig 2.53).
Figure 2.53: Molecular orbitals (BMO and ABMO)

Stability of molecules in terms of bond order
Let Nb represent the number of electrons present in the bonding orbitals and Na the
number of electrons present in the antibonding orbitals. Then
i.
ii.
iii.
If > , the molecule is stable.NbNa

If Nb < Na, the molecule is unstable.
If Nb = Na, the molecule is again unstable.
Bond order =
[Nb - Na]
The molecule is stable if Nb >Na i.e, if bond order is positive.

The molecule is unstable if Nb < Na or Nb = Na i.e, if the bond order is negative or
zero.
For diatomic molecules, the stability (as expressed in terms of bond dissociation
energy) is directly proportional to the bond order. Thus a molecule with a bond
order 3 is more stable than a molecule with a bond order 2.
Bond length is found to be inversely proportional to the bond order. Greater the
bond order, shorter is the bond length.
Addition of an electron to an antibonding molecular orbital result in an increase in
bond length and decrease in bond energy. Removal of an electron from an
antibonding molecular orbital increases the bond order and an increase in bond
energy and decrease in bond length of the resulting ion is observed.

Diamagnetic and paramagnetic nature of the molecules
If all the electrons in the molecule are paired, it is diamagnetic in nature. On the other
hand, if the molecule has some unpaired electrons, it is paramagnetic in nature.
The order of energy of molecular orbitals
The order of energy of molecular orbitals has been determined from spectroscopic data.
In simple homonuclear diatomic molecules the order is
(1s), (*1s), (2s), (*2s), (2pz), (2px) = (2py), (*2px) = (2py)
For the lighter elements boron, carbon and nitrogen, the (2px) and (2py) are probably
lower than (2pz).
For these molecules, the order is
(1s), (*1s), (2s), (*2s), (2px) = (2py), (2pz), (*2px) = (*2py) , (2pz)
Reversal in the order of and orbitals
The sequence of energy levels in which they are filled shows that (2pz) orbital has
lower energy than (2px) = (2py) molecular orbitals, i.e.,
(2pz) < (2px) = (2py)
The sequence of energy levels shown above applies to systems where mixing of ( 2s)
and (2p) atomic orbitals is negligible. This sequence applies only for O2 and F2
molecules (Fig 2.54).
Figure 2.54: Energy levels of different molecular orbitals for O2, F2 and Ne2
However, this sequence of energy levels does not apply to homonuclear diatomic
molecules of lighter elements, i.e., boron through nitrogen (Figs 2.55 and 2.56).
The difference in the energy of 2s and 2pz atomic orbitals in kJ mol-1 for the lighter
elements is given below
Li
178
Be
262
B
449
C
510
N
570
O
1430
F
1970
Figure 2.55: Mixing of atomic orbitals with same symmetry

Atomic orbitals with comparable energies can mix and form stabler atomic orbitals,
hence, molecular orbitals result from mixed s and p orbitals. The mixing is important for
elements with lower effective nuclear charge and leads to stabilization of (2s) and
(*2s) orbitals and destabilization of (2pz) and (*2pz) orbitals resulting in the reversal
of the order of the (2pz) and (2px) = (2py) oribtals.
That is,
(2px) = (2py) < (2pz).
Figure 2.56: The change in energies of MOs due to mixing of orbitals of same energy
We may now consider the formation of diatomic molecules from H2 to Ne2. Molecular
orbital theory shall give us information about the nature of homonuclear diatomic
species.
Hydrogen molecule, H2
The hydrogen molecule is formed by the combination of the hydrogen atoms. 1s orbital
of each hydrogen atom form two molecular orbitals, BMO and ABMO. Each hydrogen
atom has one electron in 1s orbital and, therefore, there are two electrons to be
accommodated in MOs. Both these electrons would be accommodated in the (1s) BMO.
The energy level diagram for H2 molecule is shown in Fig 2.57.
Figure 2.57: Energy level diagram for H2 molecule
Thus, H2 molecule will have the electronic configuration [ (1s)2]

The bond order in H2 = 1/2[2-0] = 1
Bond dissociation energy in H2 molecule is 431.4 kJ mol-1 and bond length is 74 pm.
Hydrogen molecule ion, H2+

The molecular ion has only one electron and its electronic configuration is [(1s)1] and
the bond order is (Fig 2.58).
Figure 2.58 Energy level diagrams for H2+ molecule ion and H2 molecule
The hypothetical He2 molecule
There are four electrons to be accommodated in He2 molecule. Since each molecular
orbital can accommodate two electrons with opposite spins, only one pair can be
accommodated in (1s) bonding molecular orbital and the other in (*1s) antibonding
molecular orbital.
Thus, the electronic configuration for He2 is [(1s)2 (*1s)2] and the bond order is zero.
In effect, the bonding and antibonding cancel each other and hence the molecule He2
does not exist.
Boron molecule, B2
The electronic configuration of Boron atom is 1s2 2s2 2px1.
There are ten electrons to be accommodated in B2 molecule (Fig .2.59)
Figure 2.59: Energy level diagram for B2 molecule
Energy Level Diagram for various molecules

Oxygen molecule, O2
The electronic configuration of oxygen atom is 1s2 2s2 2px2 2py1 2pz1
There are sixteen electrons to be accommodated in O2 molecule (Fig 2.60).
Figure 2.60: Energy level diagram for O2 molecule
Molecular orbital energy level diagrams showing electronic configuration of homonuclear

diatomic molecules of second period are summarized in Fig 2.61 and Table 2.13.
Figure 2.61: Molecular orbital energy level diagrams showing electronic configuration
for
Li2, Be2, B2, C2, N2, O2, F2 and Ne2
Table 2.13 The physical properties of homonuclear
diatomic
molecules of the second period
Molecule/
Bonding Anti bonding Bonds r(pm) Bond energy
Molecule Ion electrons
electrons
kJ mol-1
+
H2
1
0
0.5
106
255
H2
2
0
1
74
431.4
He2+
2
1
0.5
108
293
He2
2
2
0
-0
Li2
2
0
1
267
113
Be2
2
2
0
-0
B2
4
2
1
159
288
C2
6
2
2
131
585
N2
8
2
3
110
940
+
N2
7
2
2.5
112
~800
O2
8
4
2
121
493
O 2+
8
3
2.5
112
600
O 28
5
1.5
130
-O228
6
1
148
-F2
8
6
1
144
~150
Ne2
8
8
--0
Magnetic
property
Paramagnetic
Diamagnetic
Paramagnetic
-Diamagnetic
-Paramagnetic
Diamagnetic
Diamagnetic
Paramagnetic
Paramagnetic
Paramagnetic
Paramagnetic
Diamagnetic
Diamagnetic
--
Whatever has been studied so far in connection with molecular orbital theory can be
summarized as follows.
The positive value of bond order with H2+ ion indicates that the bond does get
formed and the molecule is stable. The molecule ion H2+ has been detected
through spectroscope when electric discharge is passed through hydrogen gas
under pressure.
The zero bond order in He2, Be2 and Ne2 molecules indicate their nonexistence. However, He2+ ion has been isolated and its existence was proved in
cosmic rays.
Surprisingly, the bond in Li2 molecule is much longer and weaker than in
H2. This may be attributed to
the 2 orbital of Li is bigger in size than 1 orbital of hydrogen and the overlap
involving orbitals of Li is less effective and diffuse.ss2s-2s
the 1s2 electrons of Li cause repulsion between the atoms and thus do not allow
two Li atoms to come nearer to each other than 2.67.
The observed paramagnetic character of B2 is explained on the basis of the
mixing of molecular orbitals of the same symmetry as discussed earlier. Due to
this mixing, the 2px and 2py molecular orbitals lie at lower energy level than
the 2pz molecular orbital. Since each bonding molecular orbital contains a
single, i.e., an unpaired electron, the molecule B2 is paramagnetic.
The molecule C2 should be stable, since 2p bonding orbitals provide four lots of
stabilization energy giving two bonds. The fact that carbon exists as
macromolecules in graphite and diamond illustrates the point that an even more
stable arrangement is formed in preference, where each atom forms four bonds.
The bond order in N2 molecule is three and thus nitrogen molecule contains a
triple bond. Hence, the nitrogen molecule is highly stable. This is confirmed by its
high bond dissociation energy (940 kJ mol-1).
Since there are two unpaired electrons (one in each) in *2px and *2py the
oxygen molecule is paramagnetic. Bond order in this case is 2 and thus oxygen
molecule contains a double bond.
Example
Of the species O2, O2+, O2-, O22-, which would have the maximum bond strength?
Solution:
The bond orders, bond lengths of the above species are in the order:
i.
Bond order: O (2.5) > O (2) > O (1.5) > O
ii.
Bond length
O22-> O2-> O2 > O2+
+ - 22 22 2
(1)
Higher bond orders are associated with shorter bond lengths and higher bond strengths.
Since O2+ has the highest bond order, it has the shortest bond length and hence the
maximum bond strength.
Bond order and bond length and bond energy of homonuclear diatomic molecules
are given below. Bond order
B2 (1) < C2 (2) < N2 (3) > O2 (2) > F2 (1)
Bond Length (pm)
B2 (159) > C2 (130) > N2 (100) < O2 (121) < F2 (144)
Bond Energy (kJ mol-1)
B2 (288) < C2 (585) < N2 (940) > O2 (493) > F2 (151)
Hence bond order is directly proportional to bond strength and inversely proportional to
bond length.
Biographic
Table 2. 13
Table 2.13 The physical properties of homonuclear
diatomic
molecules of the second period
Molecule/
Bonding Anti bonding Bonds r(pm) Bond energy
Molecule Ion electrons
electrons
kJ mol-1
H 2+
1
0
0.5
106
255
H2
2
0
1
74
431.4
He2+
2
1
0.5
108
293
He2
2
2
0
-0
Li2
2
0
1
267
113
Be2
2
2
0
-0
B2
4
2
1
159
288
C2
6
2
2
131
585
N2
8
2
3
110
940
N 2+
7
2
2.5
112
~800
O2
8
4
2
121
493
O 2+
8
3
2.5
112
600
O2
8
5
1.5
130
-O228
6
1
148
-F2
8
6
1
144
~150
Ne2
8
8
--0
Magnetic
property
Paramagnetic
Diamagnetic
Paramagnetic
-Diamagnetic
-Paramagnetic
Diamagnetic
Diamagnetic
Paramagnetic
Paramagnetic
Paramagnetic
Paramagnetic
Diamagnetic
Diamagnetic
--
Heteronuclear Diatomic Molecules

In heteronuclear diatomic molecules, the two atoms constituting a molecule are
different. The molecular orbital diagram may not be symmetrical in heteronuclear case
due to bonding between different atoms which may have different electronegativities.
The more electronegative atom will have its atomic orbitals lower in energy than the less
electronegative atom (Figure 2.62).
Figure 2.62: Molecular orbitals resulting from mixing of atomic orbitals of different
energy
The MO configurations for heteronuclear diatomic molecules are developed based on
isoelectronic principle, i.e. two molecular species with the same number of atoms and
the same total number of valence electrons are said to be isoelectronic. Isoelectronic
principle states that such molecular species will have similar molecular orbitals and
molecular structures.
Carbon monoxide CO
CO is isoelectronic with N2 molecule.
1s2 2s2 2p2
1s2 2s2 2p4
C
O
A total of 14 electrons are to be accommodated in the molecular orbitals of CO molecule

(Figure 2.63).
CO [KK (2s)2 (*2s)2 (2pz)2 (2px)2 (2py)2]
Bond order =
Thus CO contains a triple bond. Its bond dissociation energy has been found to be 1067
kJ mol-1 and bond length is equal to 114 pm.
Figure 2.63: Molecular orbital diagram for CO molecule
Nitric Oxide, NO
The electronic configuration of N and O atoms are
N
O
1s2 2s2 2p3

1s2 2s2 2p4

There are five electrons in the outer shell of N and six electrons in the outer shell of O.
Thus, a total of 11 outer electrons are to be accommodated in the molecular orbitals of
NO molecule.
Molecular Orbital Diagram of Co and No str.

NO molecule is isoelectronic with O2+ ion.
The MO configuration of NO molecule is thus
NO [KK (2s)2 (*2s)2 (2pz)2 (2px)2 (2py)2 (*2px)1]
The Bond order =

Since NO contains an unpaired electron, it is paramagnetic.
Nitrosyl ion, NO+
Removal of an electron from NO gives a nitrosyl ion NO+. The electron is removed from
the highest energy * anti bonding molecular orbital.
NO+ [KK (2s)2 (*2s)2 (2pz)2 (2px)2 (2py)2]
NO+ is isoelectronic with CO
Bond order in NO+

Bond order of three is supported by bond length of 106 pm in NO+, NO+ is diamagnetic
because of paired configuration. Loss of unpaired electron in antibonding * orbital
gives NO+ ion of higher bond energy (shortened bond)
NO+ > NO
Cyanide ion, CNCN- is isoelectronic with CO
CN- [KK (2s)2 (*2s)2 (2pz)2 (2px)2 (2py)2]
Bond order in CNHydrogen Fluoride, HF

The electronic configuration of hydrogen and fluorine are
H
1s1
F
1s2 2s2 2px2 2py2 2pz1
In the formation of molecular orbitals in HF molecule, 1s1(H) - 1s2(F), 1s1(H) - 2s2(F),
1s1(H) 2px2(F) and 1s1(H) 2py2(F) overlaps giving rise to non-bonding molecular
orbitals. Thus singly filled 2pz1 on fluorine atom overlaps with the singly filled 1s1 orbital
of hydrogen atom and forms two sigma molecular orbitals which are designated as
sp and sp*. The molecular orbital energy diagram can thus be shown as given in Fig
2.64.
HF [(1s)2 (2s)2 (spx)2 (2px)2 (2py)2]
Bond order = [2-0] = 1
Figure 2.64: Energy level diagram for HF molecule

2.4.10 Comparison Between Valence Bond Theory (VBT) and Molecular Orbital Theory
(MOT)
Common Features
Both the theories are theoretical approximations, based on quantum mechanical

model of the atom and are called modern theories of chemical bonding.
Both interpret covalent bonds as orbitals embracing two atoms.
The energies of the overlapping orbitals, according to both the theories, must be
comparable and their symmetries should be the same.
In bond formation, the orbitals of the bonding atoms must overlap according to
both the theories.
Both predict the concentration of electron density between the nuclei.
Differences
The VBT visualizes the bond formation as localized interaction between two
atomic orbitals belonging to the constituent atoms while the molecular orbital
theory involves delocalized molecular orbitals spread over the whole molecule.
While VBT fails to account for paramagnetic character of oxygen, MOT offers
satisfactory explanation.
While resonance plays an important role in VBT, this concept has no place in
MOT.
VBT is simple to apply, while MOT is difficult to apply, i.e., the calculations
involved in MOT are much more tedious than those involved in VBT.
The MO description, however, provides better descriptions of simple species such
as H2+ and O2 than do the one and three electron bonds that must be involved in
VB approach.
The MO method has the additional advantages of better describing excited states,
multiple bonding and bond weakening via occupancy of antibonding orbitals.
In summary, each approximation has its own specific uses and advantages and it is
often desirable to use the approach that is better suited to the specific situation in
question. In general, molecular orbital theory is more relevant as it considers two
possibilities of bonding, i.e., the electrons can occupy both bonding and antibonding
molecular orbitals whereas in valence bond theory the electrons represent only bonding
state.
Summary of Covalent bonding
Summary
Atoms combine in order to achieve maximum stability.

A chemical bond is a strong attractive force that exists between certain atoms in
a substance.
Lewis electron-dot formulas are simple representations of the valence shell
electrons of atoms in molecules and ions. In such formulas, the atoms usually
satisfy the octet rule.
An ionic bond is the product of the electrostatic forces of attraction between
positive and negative ions. An ionic compound consists of a large network of ions
in which positive and negative charges are balanced. The structure of a solid ionic
compound maximizes the net attractive forces among the ions.
Lattice enthalpy can be calculated using the Born-Land equation. Lattice
enthalpy is a measure of the stability of an ionic solid. Lattice enthalpy affects the
solubility of ionic compound.
Hesss law enables enthalpy changes to be determined by using Born-Haber
cycle.
Covalent character in ionic compounds occurs due to polarization of charge clouds
of ions. Cations exert great polarizing effect on the anions. Greater the
polarization, larger is the induced covalent character in an ionic compound which
is reflected in the decreasing melting points and solubility in polar solvents.
Bonds between different atoms are normally polar, and the magnitude of the
dipole moment depends on the difference in the electronegativity between the
atoms involved. The dipole moment of a molecule is the resultant of whatever
bond moments are present. The study of dipole moment is very useful for
information on percentage ionic character in a covalent bond and for elucidation
of molecular geometry of covalent molecules.
A covalent bond is a strong attractive force that holds two atoms together by
their sharing of electrons. In multiple covalent bonds, two or three pairs of
electrons are shared by two atoms.
There are two quantum mechanical approaches for covalent bond formation:
valence bond theory and molecular orbital theory.
In valence bond approach, a bond is formed by the overlap of orbitals from two
atoms. Multiple bonds occur via the overlap of atomic orbital to give sigma and pi
bonds.
By making use of the concept of hybridization, VB theory, succeeds in accounting
for the principles of molecular geometry.
Hybridization is the mixing of atomic orbitals on an atom as it interacts with

another atom. The hybridized orbitals are all of equivalent energy. Valence-shell
expansion can be explained by assuming hybridization of s, p and d orbitals.
The VSEPR model for predicting molecular geometry is based on the assumption
that valence-shell electron pairs repel one another and tends to stay as far apart
as possible. The electron pairs include bonding pairs and lone pairs. The shape of
the molecule is described by the positions of the bonding pairs only. Lone pairs
repel other pairs more forcefully than bonding pairs do and thus distort bond
angles from ideal geometry. Lone pairs take up more space than bonding pairs,
so the strength of repulsions decreases in the order:
lp-lp > lp-bp > bp-bp
The best way to describe the geometry of covalent molecule/ion is by combining
both hybridization and VSEPR theory.
Bond angles in covalent molecule/ion are influenced by factors such as electrons
on the central atom, electronegativity of the substituents, electronegativity of the
central atom etc.
By introducing the idea of resonance, the VB theory rationalizes the chemical
properties of many molecules. Resonance structures are used to explain bonding
in molecules with bonds that appear to be different in the Lewis structure but are
found to be the same experimentally.
Molecular orbital theory describes bonding in terms of the combination and
rearrangement of atomic orbitals to form orbitals that are associated with a
molecule as a whole.
The linear combination of two hydrogen 1s orbitals gives a bonding molecular
orbital and an antibonding molecular orbital.
Bonding molecular orbitals increase the electron density between the nuclei and
are lower in energy than individual atomic orbitals. Antibonding molecular orbitals
have a region of zero electron density between the new nuclei, and an energy
level higher than that of the individual atomic orbitals.
Molecular orbitals in an energy level diagram are filled using the Aufbau principle,
the Pauli exclusion principle and Hunds rule.
Molecular orbital energy level diagrams can be used to predict whether molecules
or ions exist.
Molecular orbitals of the same symmetry interact through s-p mixing. This mixing
is important for B2, C2 and N2. The molecular orbital energy level order is
different from that expected if you assume independent overlap of the s orbitals
and p orbitals.
The configuration of a diatomic molecule such as O2 can be predicted from the
order of filling of the molecular orbitals. From this configuration, we can predict
the bond order and whether the molecular substance is diamagnetic or
paramagnetic.
The MO configuration for heteronuclear diatomic molecules are developed based
on isoelectronic principle. Heteronuclear diatomics can have non-bonding orbitals,
in addition to bonding and antibonding orbitals.
Exercises
1. Why do atoms combine in a definite and not in an arbitrary number to form a
given molecule?
2. (Water is H2O but neither H3O nor HO2).
3. Explain why H2 is a stable molecule formed from two hydrogen atoms while He2 is
unstable?
4. Write Lewis structures for N2, C2, O3, PO43-, SO42- and HClO4.
5. Oxalic acid,
, is a poisonous substance found in uncooked spinach
leaves. If oxalic acid has a

6. Dichlorodifluoromethane, CCl2F2, is a gas used as a refrigerant and aerosol
propellant. It is also known commercially as one of the freons. Write the Lewis
formula for CCl2F2.
7. Why is hydrogen an exception to octet rule?
8. Distinguish clearly between bond energy and 'bond dissociation energy', giving
numerical values and units for the energy terms in each instance.
9. Define lattice enthalpy of an ionic solid. Write the Born-lande equation and give
the significance of the terms involved in it.
10. Calculate the lattice enthalpy of NaCl using the following data:
11. Enthalpy of sublimation of Na (s) = +108.3 kJ mol-1
12. Enthalpy of dissociation of Cl2 (g) = +119.7 kJ mol-1
13. Ionization enthalpy of Na (g)
= + 493.3 kJ mol-1
14. Electron gain enthalpy of Cl (g)
= - 361.9 kJ mol-1

15. Enthalpy of formation of NaCl (s) = - 410.9 kJ mol-1
16. What is Madelung constant? Does it depend upon the geometry of an ionic solid?
17. Give reasons why?
18. a) BaSO4 is insoluble in water.
19. b) melting point of BaO is high.
20. c) Noble gases do not form ionic halides.
21. d) KCl2 is not formed.
22. What is Born-Haber cycle? Using Born-Haber cycle, calculate the electron affinity
of chlorine from the following data:
23. Bond enthalpy of Cl2
= + 240.0 kJ mol-1
24. Enthalpy of formation of NaCl(s)
= 440.0 kJ mol-1
25. Enthalpy of sublimation of Na(s)
= + 110.0 kJ mol-1
26. Enthalpy of ionization of Na(g)
= + 480.0 kJ mol-1
27. Enthalpy of lattice formation of NaCl(s) = 810.0 kJ mol-1
28. Comment on
29. NaCl exists but NaCl2 does not, CaF2 exists but CaF does not.
30. The stabilization of noble gas configuration is meaningless since the formation of
O2-, S2-, Li+, Na+ etc., are endothermic.
31. Although the lattice energy is high for AgCl (-910 kJ mol-1), yet the heat of
formation is much less (fH = -127 kJ mol-1).
32. Explain the effect of polarizing power and polarizability on the properties of ionic
compounds.
33. What is meant by partial ionic character of a covalent bond? What are its
consequences?
34. Describe Fajans rules. How does it explain the relative covalent/ionic nature of
the following pairs of compounds
35. FeCl2, FeCl3
36. LiI, CsI
37. CuCl, NaCl
38. Explain why
39. Melting point of NaCl is higher than that of AlCl3?
40. Stability of alkaline earth carbonates increases with increase in size of alkaline
earth metal.
41. ZnCl2 is soluble in organic solvents and MgCl2 is insoluble.
42. Which compound of each of the following pairs is more covalent?
43. AgCl or AgI
44. LiCl or KCl
45. MgCl2 or BeCl2
46. CaCl2 or CdCl2
47. ZnO or ZnS
48. NaF or CaO
49. Which of the following molecules would you predict to be polar?
50. H2S, BCl3, CCl4, C2H6, CO2
51. The dipole moment of HCl molecule is known to be 1.03 D and the bond distance
HCl is 1.27. Calculate the percentage ionic character in HCl.
52. (Ans: 17%)
53. Explain why CO2 has zero dipole moment while SO2 has 1.6 D.
54. Which of the following molecules have zero dipole moment and why?
55. (i) benzene
(ii) p-dichlorobenzene
56. (iii) p-dihydroxybenzene
(iv) chlorobenzene
57. The dipole moment of NF3 is much less than that of NH3 though both have same
structure. Explain.
58. The dipole moments of NH3 and NF3 are in opposite directions. Explain.
59.
60. Using hybridization concept, describe the bonding in C2H6, C2H4, C2H2 and
O=C=O
61. Predict the type of hybridization and shape of the following species using valence
bond theory:
62. ICl463. CO3264. Xe2F2
65. ClF3
66. Predict the shapes of the following molecules using valence bond theory
67. NO368. SF4
69. XeF6
70. What is VSEPR theory and what are its limitations?
71. Predict the shapes of the following molecules or ions on the basis of VESPR
theory
72. I373. BF4-

74. NH4+
75. XeF2
76. SiCl4
77. On the basis of VSEPR theory, write the possible structures of ClF3 and predict
the most favoured structure showing your arguments.
78. State the d-orbitals involved in sp3d, sp3d2 and sp3d3 hybridizations.
79. Describe the shapes of
80. ClO381. CO32- and
82. I3- ions on the basis of hybridization.
83. Explain the concept of resonance and resonance energy.
84. The nitrate ion has three equivalent oxygen atoms, and its electronic structure is
a resonance hybrid of three electron dot structures. Draw them.
85. What are the conditions of resonance (selection rules)? Draw as many electrondot resonance structures as possible for each of the following molecules or ions,
giving all atoms octets:
86. SO2
87. CO3288. BF3
89. Nitrous oxide (N2O), called laughing gas, is sometimes used by dentists as an
anaesthetic. Given the connections NNO draw two electron-dot resonance
structures for N2O.
90. Describe the potential energy diagram for H2 molecule and deduce various
postulates of valence bond theory.
91. Briefly discuss the concept of LCAO to produce molecular orbitals.
92. What are bonding and antibonding molecular orbitals? Explain with examples.
93. Using LCAO method, draw the shapes of p-p combination of atomic orbitals, both
axial as well as sideways.
94. Draw the molecular orbital energy level diagrams for the following molecules/
ions and predict their bond order and magnetic character
95. B2
96. C2
97. NO
98. NO+
99. CN100.
Write the molecular configuration of O2, O2+, O2- and O22- and arrange
them in increasing order of their bond length and bond strength.
101.
Indicate the effects of the following ionization process and bond orders
and bond lengths
102.
i) O2 + e- O2103.
ii) N2 e- N2+
104.
Why does CO form numerous metal complexes while the isoelectronic
nitrogen molecule does not? Explain on the basis of MO theory.
105.
NO can readily lose electron to form NO+ ion. Explain Why?
106.
Draw molecular orbital diagram for CO molecule.
107.
Explain
108.
Geometries of HO, HS, HSe are the same but the bond angles are HO >
HS > HSe222222
109.
All P-F bonds in PF5 are not equivalent
110.
The bond angles in phosphorus compounds are PF3< PCl3 < PBr3< PI3 and
PF3 > PH3
111.
NCl5 does not exist while PCl5 exists.
112.
PCl5 exists but PH5 does not.
113.
Sulphur forms SF6 but oxygen does not form OF6 or SCl6 or SH6.
114.
Explain
115.
NF is pyramidal but BF is planar.33
116.
BeCl2 is linear, CO2 is linear but SO2 is bent.
117.
The bond angle in F2O is smaller than that in H2O
118.
Compare and contrast valence bond theory and molecular orbital theory.
119.
120.
single bond and no C-H bond, draw its electron dot structure.
References
Book References
Inorganic Chemistry,
Principles of Structure and Reactivity
James E. Huheey et al.
Addison-Wesley Publishing Company
Advanced Inorganic Chemistry
F. Albert Cotton et al.

J.Wiley & Sons
Models in Structural Inorganic Chemistry
A.F. Wells
Oxford University Press, London (1970).
Inorganic Chemistry
Therald Moeller
John Wiley & Sons
Concise Inorganic Chemistry
J.D. Lee
Blackwell Science Ltd., London
Concepts and Models of Inorganic Chemistry
Bodie Douglas, Dare Mc. Danial, John Alexander
Wiley-India
Inorganic Chemistry
Gary L. Miesslar Donald A. Tarr
Pearson Education (Singapore) Pvt. Ltd.
Chemistry: Molecules, Matter and Change
Peter Atkins, Loretta Jones
W.H. Freeman and Company, New York
Chemistry
John Mc Murry, Robert C. Fay
Pearson Education Chemistry
Chemistry
Raymond Chang
Mc Graw-Hill Publishing Company
Inorganic Chemistry
Peter Atkins, Tina Overton
Oxford University Press
Advanced Chemistry
Philip Mathews
Cambridge University Press
Principles of Inorganic Chemistry
B. R. Puri, L. R. Sharma, K. C. Kalia
Vallabh Publications, Delhi 110088
Inorganic Chemistry
Ramesh Kapoor, S. K. Vashisht, R. S. Chopra
R. Chand & Co., New Delhi 110002
Valence and Molecular Structure
Cartmell, E. and Fowels, G.W.A
ELBS and Butterworth, London
J.D.Lee : A New Concise inorganic Chemistry, E.L.B.S
F.A.Cotton & G.Wilkinson: Basic Inorganic Chemistry, John Wiley.
Web Side References
14. http://www.visionlearning.com/library/module_viewer.php?mid=55 (chemical

bonding)
15. http://pages.towson.edu/ladon/carbon.html (hybridization in carbon)
16. http://www.intute.ac.uk/sciences/reference/plambeck/chem1/p02201.htm
17. http://chemed.chem.purdue.edu/genchem/topicreview/bp/ch8/mo.html
(molecular orbital theory)
18. http://www.chem.qmul.ac.uk/software/download/mo/ (molecular orbital theory)
Glossary
Born-Haber cycle- It is an indirect way to calculate the lattice enthalpy which

is difficult to calculate directly. It is based on Hesss law.
Covalent Bond- It involves the sharing of a pair of electrons between two
atoms.
Fajans rules- An ionic compound will have a high degree of covalency if the
positive ion is small and highly charged and the negative ion is large.
Hesss law- Hesss law states that the enthalpy of a reaction is the same,
whether it takes place in a single step or in more than one step.
Hybridization- Is the mixing of atomic orbitals in an atom (usually a central
atom) to generate a set of new atomic orbitals called hybrid orbitals. Hybrid
orbitals are used to form covalent bonds.
Ionic Bond It involves the complete transfer of one or more electrons from one
atom to another.
Lewis octet rule -Each atom shares electrons with neighbouring atoms to
achieve a total of eight valence electrons.
Limitations to octet rule- It fails to account for the stability of incomplete

octet, expanded octet, odd-electron and shape of a molecule.
Lattice- The ion exists in three dimensional arrays, which we call the lattice. The
lattice energy is a measure of the energetic stability of the crystal.
Lattice Enthalpy- Is defined as the energy released when one mole of the
compound is formed in the regular lattice structure from requisite number of
ions.
Linear Combination of Atomic Orbitals (LCAO)-According to this approach
the atomic orbitals (on different atoms) of comparable energies and of
appropriate symmetry combine (merge) to give rise to an equal number of
molecular orbitals. Atomic orbitals of constituent atoms combine in a linear
(additive) fashion to form molecular orbitals.
Metallic Bond It involves the free movement of valency electron throughout
the whole crystal and it is also characterised by small difference in
electronegativity.
Molecular orbital method-All the orbitals in the ion or molecule are assumed to
take part in bonding. The individual orbitals are combined to give the molecular
orbitals, which may stretch over the entire molecule.
Polarisibilty- When a large negative ion is put near to the small negative ion,
since the outer electrons of the large ion are far from nucleus, they are not held
very tightly. They will be attracted towards the positive ion. The charged cloud of
negative ion will be distorted. This is called the polarization of negative ion by
positive ion.
Polarisibile-Anions are large in size than cations and, therefore, their electron
clouds are less tightly held. When two oppositely charged ions approach each
other closely, the positively charged cation attracts the outer most electrons of
the anions and repels its positively charged nucleus. This results in the distortion
or polarisation of the anion.
Polarizing power-The power of an ion to distort the other ion is known as its
polarizing power.
Resonance- When a compound cannot be assigned by one single structure then
closely resembling structures are drawn to explain all their properties. These
closely resembling structures are known as resonating structures and the
phenomenon is known as resonance.
Valance bond approach- Covalent bond may be seen as accumulation of high
charge density in the internuclear region resulting from the overlapping of atomic
orbitals. The strength of the bond depends on the extent of the overlapping,
greater the overlapping stronger the bond.

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Chapter 2: Chemical Bonding and Molecular Structure

B.Sc (Prog.) 1st Year

Fellow: Dr. V. C. Rao, Associate Professor

Institute of Lifelong Learning, University of Delhi

Chapter 2: Chemical Bonding and Molecular Structure

Institute of Lifelong Learning, University of Delhi

Chapter 2: Chemical Bonding and Molecular Structure

2.2 Preliminary Survey

Figure 2.2: Lewis structures

of the quantum-mechanical approaches provide quantitative

Institute of Lifelong Learning, University of Delhi

Chapter 2: Chemical Bonding and Molecular Structure

Ionic compounds usually exist as crystalline solids. X-ray diffraction patterns of

Institute of Lifelong Learning, University of Delhi

Chapter 2: Chemical Bonding and Molecular Structure

Structure of ionic solids

The radius ratio

Table 2.1 Radius Ratio and Geometry of Ionic Solids

2.3.1 Lattice Enthalpy (Lattice Energy) Lattice

Institute of Lifelong Learning, University of Delhi

Chapter 2: Chemical Bonding and Molecular Structure

Figure 2.5: Clustring of ion pairs to form ionic solid

Clustering of Ion- Pairs to form Ionic Solids

Institute of Lifelong Learning, University of Delhi

Chapter 2: Chemical Bonding and Molecular Structure

Consider NaCl crystal having face centered cubic (FCC) structure.

Figure 2.6: The crytal structural of NaCl (Rock Salt)

Lattice enthalpy is defined as positive;

Institute of Lifelong Learning, University of Delhi

Chapter 2: Chemical Bonding and Molecular Structure

Lattice Enthalpy (kJ mol-1)

Madelung Constant Values for Some Common Ionic Solid

Na+(6); Cl- (6)

Cs+ (8); Cl-(8)

Zn2+(4); S2- (4)

Ca2+ (8); F-(4)

Institute of Lifelong Learning, University of Delhi

Chapter 2: Chemical Bonding and Molecular Structure

RbF > CsF

(2200 kJ mol-1) > CaCl (720 kJ mol-1)

Institute of Lifelong Learning, University of Delhi

Chapter 2: Chemical Bonding and Molecular Structure

Hhydration (kJ mol-1)

Institute of Lifelong Learning, University of Delhi

Chapter 2: Chemical Bonding and Molecular Structure

Figure 2.7: A Schematic Representation of Born-Haber Cycle for the Formation

Figure 2.8: A Schematic Representation of Born-Haber Cycle for the Formation

H1= 108.4 kJ mol-1

Applying Born-Haber cycle, we have

Institute of Lifelong Learning, University of Delhi

Chapter 2: Chemical Bonding and Molecular Structure

Close agreement between theoretical values (assuming ionic bonding) and

Enthalpy of dissociation for

Cl2 (g) Cl (g)

H2= + 122 kJ mol-1

Electron gain enthalpy for

Cl2 (g) +e- Cl- (g)

H4= - 355 kJ mol-1

Enthalpy of formation for

Cl2 (g) KCl (s)

Institute of Lifelong Learning, University of Delhi

Chapter 2: Chemical Bonding and Molecular Structure