Chemical Bonding

Chemical bond: A chemical bond is an attractive force that holds

atoms together in different chemical species such as molecules, ions
and so on.

 Why are most atoms chemically bonded to each other?

 As independent particles, atoms are at relatively high potential

energy.
 However, Nature always favors the arrangements in which potential
energy is minimize.
 The atoms are in less stable state by themselves before they are
combine.
 By bonding with each
other, atoms decrease
in potential energy,
thereby creating more
stable arrangements
of matter.
 Types of Chemical bond
 Ionic bond: An ionic bond is a chemical bond formed by the
electrostatic attraction between positive and negative charged ions
Na (1s22s22p63s1)  Na+(1s22s22p6) + e-
Cl (1s22s22p63s13p5) + e-  Cl- (1s22s22p63s23p6)
 Formation of ionic compounds
Na readily gives up 1e- and chlorine accept that electron and thereby
positively charge Na+ and negatively charged Cl- ions are formed.
Then by electrostatic forces of attraction these two oppositely charged
ions are joined to form ionic compounds.
The factors favoring for the formation of an ionic bonds are:
 (1) Number of valence electrons: The atom A should possess 1,
2 or 3 valence electrons, while the atom B should have 5, 6 or 7
valence electrons. The elements of group IA, IIA and IIIA satisfy
this condition for atom A and those of groups VA, VIA, and
VIIA satisfy this condition for atom B.
 (2) Net lowering of Energy: To form a stable ionic compound,
there must be a net lowering of the energy. In other words
energy must be released as a result of the electron transfer and
formation of ionic compound by the following steps :
i. The removal of electron from atom A (A – e– → A+) requires
input of energy, which is the ionization energy (IE). It should
be low.
ii. The addition of an electron to B (B + e– → B– ) releases energy,
which is the electron affinity of B (EA). It should be high.
iii. The electrostatic attraction between A+ and B– in the solid
compound releases energy, which is the electrical energy. It
should also be high.
If the energy released in steps (b) and (c) is greater than the energy
consumed in step (a), the overall process of electron transfer and
formation of ionic compound results in a net release of energy.
Therefore, ionization of A will occur and the ionic bond will be
formed. For example, in case of formation of sodium chloride
(NaCl), we have
Na → Na+ + e– H = 119 kJ
Cl + e– →Cl– H = -85 kJ
Na+ +Cl– → Na+Cl– H = -187 kJ
The net enthalpy changed Hnet = +119–187–85 = –153 kcal. Since
the overall process results in a lowering of energy, the ionic bond
between Na and Cl will be formed
 (3) Electronegativity difference of A and B
From the line of argument used in (2), we can say that if atoms A
and B have greatly different electronegativities, only then they will
form an ionic bond. In fact, a difference of 2 or more is necessary for
the formation of an ionic bond between atoms A and B. Thus Na has
electronegativity 0.9, while Cl has 3.0.
Since the difference is (3.0 – 0.9) = 2.1, Na and Cl will form an ionic
bond.
 (4) Size of the ions
In order to have the greater force of attraction between the
cations and anions their size should be small as the force of
attraction is inversely proportional to the square of the
distance between them.
 (5) Charge on Ions
Greater the charge on ions greater will be the force of
attraction between them and, therefore, greater will be the
strength of the ionic bond.
 Covalent bonding  results from the sharing of electron
pairs between two atoms
 In purely covalent bond, electrons shared equally between two
atoms
The factors favoring for the formation of covalent bonds are :
(1) Number of valence electrons
Each of the atoms A and B should have 5, 6 or 7 valence electrons so
that both achieve the stable octet by sharing 3, 2 or 1 electron-pair. H
has one electron in the valence shell and attains duplet. The non-
metals of groups VA, VIA and VIIA respectively satisfy this
condition.
(2) Equal electronegativity
The atom A will not transfer electrons to B if both have equal
electronegativity, and hence electron sharing will take place. This can
be strictly possible only if both the atoms are of the same element.
(3) Equal sharing of electrons
The atoms A and B should have equal (or nearly equal) electron
affinity so that they attract the bonding electron pair equally. Thus
equal sharing of electrons will form a nonpolar covalent bond. Of
course, precisely equal sharing of electrons will not ordinarily occur
except when atoms A and B are atoms of the same element, for no two
elements have exactly the same electron affinity.
 Degree of bonding between
atoms of 2 elements being ionic
or covalent estimated by
calculating difference in
elements’ ENs
 Fluorine’s EN = 4.0, Cesium’s
EN = 0.7
 4.0-0.7 = 3.3
 According to table, F-Cs is
ionic
 The greater the difference, the
more ionic the bond
 Nonpolar-covalent Bonds
 Nonpolar-covalent bond  a covalent bond
in which the bonding electrons are shared
equally by the bonded atoms, resulting in a
balanced distribution of electrical charge
 0-5% ionic character (0-0.3 EN difference) is
nonpolar-covalent bond
Polar-covalent Bonds
 Polar-covalent bond  covalent bond in
which the bonded atoms have an unequal
attraction for the shared electrons
 Bonds that have significantly different Ens,
electrons more strongly attracted by more-EN
atom
 These bonds are polar  they have an uneven
distribution of charge
Formation of Covalent Bond with potential energy diagram
 Bonded atoms have lower potential energy than unbonded atoms
 At large distance atoms don’t influence each other and potential
energy set at 0 at this stage.
 Consider formation of hydrogen molecules(H2); Each H has (+)
proton and nucleus surrounded by (-) electron
 As atoms near each other, charged particles start to interact
 Approaching nuclei and electrons are attracted to each other and
decrease in total potential energy
 The amount of attraction/repulsion depends
on how close the atoms are to each other
 When atoms first “see” each other,
electron-proton attraction stronger than e-e
or p-p repulsions
 So atoms drawn to each other and potential
energy lowered
 Attractive force dominates until a distance
is reached where repulsion equals attraction
 As long as energy stays close to minimum
they stay covalently bonded (Valley of the
curve)
 Closer the atoms get, potential energy rises
sharply
 Repulsion becomes greater than attraction
 The Octet Rule

 Noble-gas atoms have minimum energy existing on their own

electron configurations
 Outer orbitals completely full
 Bond formation follows octet rule  chemical compounds
tend to form so that each atom, by gaining, losing, or sharing
electrons, has an octet of electrons in its highest occupied
energy level
Example: Bonding of Fluorine
 2 F atoms bond to form F2
 7 e- in highest energy level

Example: HCl
 Limitation of Octet Rule
 Most main-group elements form covalent bonds according to
octet rule
 It is clear that octet rule is based upon the chemical inertness of
noble gases. However, some noble gases ( Xe, Kr) also combine
with oxygen and fluorine to form a number of compounds like
XeF2, KrF2, XeOF2 etc. This theory does not account for the
shape of molecules.
 Incomplete octet of the central atom e.g. H-H only 2 electrons
 Boron, B, has 3 valence electrons ([He]2s22p1) and boron tends
to form bonds where it is surrounded by 6 e- (e- pairs)
 The Expanded Octet: Elements in and beyond the third period of
the periodic table have, apart from 3s and 3p orbitals, 3d orbitals
also available for bonding. In a number of compounds of these
elements there are more than eight valence electrons around the
central atom. This is termed as expanded octet.Examples-PF5,
SF , H SO
 Lewis Structures

 Lewis structures  formulas in which atomic symbols represent nuclei

and inner-shell electrons, dot-pairs or dashes between two atomic
symbols represent electron pairs in covalent bonds, and dots next to only
one atomic symbol represent unshared electrons

H H H H
 Pair of dots representing shared pair in covalent bond often replaced by
long dash
 Resonance structures
 According to the concept of resonance, whenever a single Lewis
structure cannot describe a molecule accurately, a number of
structures with similar energy, position of nuclei, bonding and non-
bonding pairs of electrons are taken as the canonical structures of
the hybrid which describes the molecule accurately.
 For example, O3 molecule can be
represented by two structures as
shown in the figure.
 For O3 these two structures
constitute the canonical structures
or resonance structures and their
hybrid shown by the third figure
represents the structure of o3 more
accurately. this is called resonance
hybrid.
 Fajan’s rules
The partial covalent character of ionic bonds was discussed by
Fajan’s in terms of the following rules:
• The smaller the size of the cation and the larger the size of the
anion, the greater the covalent character of an ionic bond.
• The greater the charge on the cation, the greater the covalent
character of the ionic bond.
• For cations of the same size and charge, the one, with electronic
configuration (n-1)dnnso, typical of transition metals, is more
polarising than the one with a noble gas configuration, ns2 np6,
typical of alkali and alkaline earth metal cations. The cation
polarises the anion, pulling the electronic charge toward itself and
thereby increasing the electronic charge between the two. This is
precisely what happens in a covalent bond, i.e., build-up of
electron charge density between the nuclei. The polarising power
of the cation, the polarisability of the anion and the extent of
distortion (polarisation) of anion are the factors, which determine
the per cent covalent character of the ionic bond.
 Metallic Bonding
 Metallic bonding is the type of bonding found in metallic elements.
This is the electrostatic force of attraction between positively
charged ions and delocalized outer electrons.
 Metallic bonding refers to the interaction between the delocalized
electrons and the metal nuclei.
 As the metal cations and the electrons are oppositely charged, they
will be attracted to each other, and also to other metal cations.
These electrostatic forces are called metallic bonds, and these are
what hold the particles together in metals.
 Metallic-Bond Model
 Highest energy levels of most metal atoms only occupied by
few e-
 Ex. s-block metals have one or two valence e- where all 3 p
orbitals are empty
 d-block metals have many empty d orbitals just below highest
energy level
 Within metal, empty orbitals in outer energy levels overlap
 Allows outer e- to move freely
 e- are delocalized  do not belong to any one atom
 Metallic bonding  chemical bonding that results from
attraction between metal atoms and surrounding sea of
electrons
 Hydrogen bonds
A hydrogen bond is the attractive force between the hydrogen
attached to an electronegative atom of one molecules and an
electronegative atom of a different molecules. Usually the
electronegative atom is oxygen, nitrogen, fluorine and chlorine, which
has a partial negative charge.
In compounds of hydrogen with strongly electronegative elements,
such as fluorine, oxygen and nitrogen, electron pair shared between
the two atoms lie far away from the hydrogen atom. As a result, the
hydrogen atom becomes highly electropositive with respect to the
other atom. Such a molecule is said to be polar . The molecule
behaves as a dipole because one end carries a positive charge and the
other end a negative charge. The electrostatic force of attraction
between such molecules should be very strong. This is
because the positive end of one molecule is attracted by the negative
end of the other molecule . Thus, two or molecules may associate
together to form larger cluster of molecules.
 Types of hydrogen bonding
 Intermolecular hydrogen bonding: This type of hydrogen bonding
involves electrostatic forces of attraction between hydrogen and
electronegative element of two different molecules of the substance.
Hydrogen bonding in molecules of HF, NH3 , H2O etc. are examples
of intermolecular hydrogen bonding.
 Intramolecular hydrogen bonding
This type of bonding involves electrostatic forces of attraction
between hydrogen and electronegative element both present in the
same molecule of the substance. Examples o-nitrophenol and
salicylaldehyde.
 p-Nitrophenol , on account of large distance between two groups ,
does not show any intramolecular hydrogen bonding. On the other
hand, it shows the usual inter molecular hydrogen bonding , as
illustrated below:
 Valence Shell Electron Pair Repulsion Theory
The main postulates of VSEPR theory are as follows:
 The shape of a molecule depends upon the number of valence
shell electron pairs (bonded or non-bonded) around the central
atom.
 Pairs of electrons in the valence shell repel one another.
 These pairs of electrons tend to occupy such positions in space
that minimise repulsion and thus maximise distance between them.
 The repulsive interaction of electron pairs decrease in the order:
Lone pair (lp) – Lone pair (lp) > Lone pair (lp) – Bond pair (bp) >
Bond pair (bp) – Bond pair (bp).
 The lone pairs are localised on the central atom, each bonded pair
is shared between two atoms. As a result, the lone pair electrons in
a molecule occupy more space as compared to the bonding pairs
of electrons. This results in greater repulsion between lone pairs of
electrons as compared to the lone pair – bond pair and bond pair –
bond pair repulsions. These repulsion effects result in deviations
from idealised shapes and alterations in bond angles in molecules.
 Valence Shell Electron Pair Repulsion Theory
 if there are only two electron pairs in the valence shell of an atom,
these pairs tend to be at opposite sides of the nucleus, so that
repulsion is minimized. This gives a linear arrangement of electron
pairs; that is, the electron pairs mainly occupy regions of space at an
angle of 180 to one another.
 If three electron pairs are in the valence shell of an atom, they tend
to be arranged in a plane directed toward the corners of a triangle of
equal sides (equilateral triangle). This arrangement is trigonal
planar, in which the regions of space occupied by electron pairs are
directed at 120 angles to one another.
 Four electron pairs in the valence shell of an atom tend to have a
tetrahedral arrange- ment. That is, if you imagine the atom at the
center of a regular tetrahedron, each region of space in which an
electron pair mainly lies extends toward a corner, or vertex (Figure
10.2). (A regular tetrahedron is a geometrical shape with four faces,
each an equi- lateral triangle. Thus, it has the form of a triangular
pyramid.) The regions of space mainly occupied by electron pairs
are directed at approximately 109.5 angles to one another.
 Valence Shell Electron Pair Repulsion Theory

 Five electron pairs tend to have a trigonal bipyramidal

arrangement. The electron pairs tend to be directed to the
corners of a trigonal bipyramid, a figure formed by placing the
face of one tetrahedron onto the face of another tetrahedron.
 Six electron pairs tend to have an octahedral arrange- ment.
The electron pairs tend to be directed to the corners of a regular
octahedron, a figure that has eight triangular faces and six
vertexes, or corners.
 Molecular orbital theory is a theory of the electronic
structure of molecules in terms of molecular orbitals,
which may spread over several atoms or the entire
molecule.
Major postulates of the theory are:
(i) The wave function of an electron in a molecule is
called molecular orbital (MO). The molecular orbital
surrounds all the nuclei in the molecule.
(ii) The atomic orbitals (AO’s) of nearly equal energy,
and appropriate symmetry combine to give equal
number of MO’s. The MO’s are constructed by the
linear combination of the atomic orbitals (LCAO
method).
(iii) MO of lower energy is called bonding molecular
orbital (  b ), while that of higher energy as
antibonding molecular orbital ( a ),
(v) The electrons of the constituent atoms of a molecule are
distributed over all the available MO’s in accordance with
the Aufbau principle, the Pauli's exclusion principle and
Hund’s rule.
(vi) Like atomic orbitals (AO’s), the molecular orbitals can
also be arranged according to their energies.
 Consider the H2
Each H atom has a 1s atomic orbital. When two H atoms come to a
proper proximity, their 1s orbitals interact and produce two
molecular orbitals: a bonding MO and an anti-bonding MO.
If the electrons are in phase, they have a constructive interference.
This results in a bonding sigma MO (σ1s). This MO has an increased
probability of finding electrons in the bonding region.
If the electrons are out of phase, they have a destructive
interference. This results in an anti-bonding sigma MO (σ*1s). This
MO has a decreased probability of finding electrons in the bonding
region. (Valence Bond Theory does not explain this phenomenon.)

Schematic representation of the bonding molecular orbital σ(1s)

Molecular orbitals that are concentrated in regions between
nuclei are called bonding orbitals. The antibonding orbital in H2 ,
is denoted 𝜎1s.
Molecular orbitals having zero values in the region between two
nuclei and therefore concentrated in other regions are called
antibonding orbitals. The antibonding orbital in H2, is denoted
𝜎1s*.

Electronic configaration
(𝜎1s)2 (𝜎*1s)0
 Conditions For the Formation of MOs
Formation of MOs by the combination of atomic orbitals
takes place only if the following conditions are satisfied:
(i) The combining atomic orbitals should have nearly
equal energies. Only the atomic orbitals of nearly the
same energy combine to form MOs. For example, 1s
atomic orbitals of two atoms can combine to form one
bonding ( 1s ) and one antibonding ( * 1s ) orbitals. The
1s atomic orbital of one atom cannot combine with 2s or
2p atomic orbital of the other atom.
(ii) The combining atomic orbitals should have the same
symmetry. The atomic orbitals are oriented in space.
Only those atomic orbitals can combine to form molecular
orbitals which have the same symmetry about the
molecular axis. For example, a p x orbital of an atom can
combine with a p x orbital of another atom. A p x orbital
cannot combine with a p z orbital.
(iii) The combining atomic orbitals should overlap
effectively. MOs are formed only if the combining atomic
orbitals overlap to a reasonable extent.
The presence of one or more unpaired electrons accounts for
the paramagnetic nature of the molecule.
The electronic configuration in which all the electrons are
paired indicate the diamagnetic nature of the species.
The strength of a chemical bond is described in terms of a
parameter called bond order.
As per definition, the bond order is expressed as,
Bond order = (No. of electrons in BMO-No. of electrons in
ABMO)/2
=(Nb-Na)/2
where, N b is the total number of electrons in bonding MOs.
N a is the total number of electrons in antibonding MOs.
(a) When, N b > N a : Bond order > 0 (+ ve). Then, a stable
bond formation is indicated.
(b) When, N b =N a : Bond order =0. Then, the bond is
unstable. In fact. such a bond is not formed.
Electronic configaration = KK(𝜎2s)2 (𝜎*2s)2 (𝜎2p)2 (𝛑2p)2(𝛑2p)2 (𝛑 *2p)1 (𝛑*2p)1(𝜎*2p)0
The ( 1s)2( *1s)2 part of the configuration is often abbreviated KK

Bond order = (8-4)/2 = 2, There are two unpaired two electron on the
antibonding orbital, therefore, O2 is paramagnetic in nature.
 Examples of molecular orbitals

Electronic configaration = KK(𝜎2s)2 (𝜎*2s)2 (𝜎2p)2 (𝛑2p)2(𝛑2p)2 (𝛑 *2p)0 (𝛑*2p)0(𝜎*2p)0

Bond order = (8-2)/2 = 3, There are no unpaired electron on the orbital,

therefore, O2 is diamagnetic in nature
One minor complication that you should be aware
of is that the relative energies of the  and p
bonding molecular orbitals are reversed in some of
the second-row diatomics.