Chemical Bonding

Chemical Bond

A chemical bond is defined as a force that acts between two

or more atoms to hold them together as a stable molecule.

There are three different types of bonds recognized by chemists:

(1) Ionic or Electrovalent bond.
(2) Covalent bond.
(3) Coordinate covalent bond.

Definition of Valence
The term valence (or valency) is often used to state the potential
or capacity of an element to combine with other elements.
Valence is the number of bonds formed by an atom in a molecule.
 Valence Electrons
The electrons in the outer energy level of an atom are the ones that
can take part in chemical bonding. These electrons are, therefore,
referred to as the valence electrons.

The electronic configuration of Na is 2, 8, 1 and that of Cl is 2, 8, 7.

Thus sodium has one valence electron and chlorine 7. It is
important to remember that for an A group element of the periodic
table (H, O, K, F, Al etc.) the group number is equal to the number of
valence electrons.

Bonding and Non-bonding Electrons

The valence electrons actually involved in bond formation are

called bonding electrons. The remaining valence electrons still
available for bond formation are referred to as non-bonding
electrons. Thus:
Electronic theory of valence

The theory states that : In chemical bond formation, atoms interact

by losing, gaining, or sharing of electrons so as to acquire a stable
noble gas configuration. Each noble gas, except helium, has a
valence shell of eight electrons
The electronic theory of valence could well be named as the Octet
theory of Valence. It may be stated as : Atoms interact by electron-
transfer or electron-sharing, so as to achieve the stable outer shell of
eight electrons.

Ionic bond:
The electrostatic attraction between the cation (+) and anion (–)
produced by electron-transfer constitutes an Ionic or Electrovalent
bond.
Conditions for formation of ionic bond:

The conditions favorable for the formation of ionic bond 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) Electronegativity difference of A and B

Atoms A and B if they have greatly different electro negativities, 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.
Factors governing the formation of ionic bonds:

(1) Ionization energy:

The ionization energy of the metal atom which looses electron(s)

should be low so that the formation of +vely charged ion is easier.
Lower the ionization energy greater will be the tendency of the
metal atom of change into cation and hence greater will be the ease
of formation of ionic bond. That is why alkali metals and alkaline
earth metals form ionic bonds easily.

(2) Electron affinity:

The atom which accepts the electron and changes into anion should
have high electron affinity. Higher the electron affinity more is the
energy released and stable will be the anion formed. The elements
of group VI A and VII A have, in general, higher electron affinity and
have high tendency to form ionic bonds.
 (3) Lattice Energy:

The amount of energy released when one mole of an ionic

compound is formed from its cations and anions is called the
lattice energy.

Greater the lattice energy, greater the strength of ionic bond.

The value of lattice energy depends upon the following two
factors:
(a) 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.

(b) 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.
 Some examples of ionic compounds are: NaCl, MgCl2, CaO
and Al2O3 etc.
Characteristics of ionic compounds:

(1) Solid at room temperature

(2) High melting point
(3) Hard and brittle
(4) Soluble in water
(5) Conductor of electricity
(6) Do not exhibit isomerism
(7) Ionic reactions are fast.

Covalent bond:

The attractive force between atoms created by sharing of an

electron-pair.
Conditions for formation of covalent bond:

The conditions favorable for the formation of covalent bond 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 electron

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.

Some examples of ionic compounds are: H2, Cl2, H2O and NH3
etc.
Characteristics of covalent compounds:
(1) Gas, liquids or solid at room temperature.
(2) Low melting points and boiling points.
(3) Neither hard nor brittle
(4) Soluble in organic solvents
(5) Non conductor of electricity
(6) Exhibit isomerism
(7) Covalent reactions are slow.
 Co-ordinate Covalent bond:

A covalent bond in which both electrons of the shared pair come

from one of the two atoms (or ions). The compounds containing a
coordinate bond are called coordinate compounds.

SOME EXAMPLES OF COORDINATE COMPOUNDS OR IONS:

Lewis structures of some common molecules or ions
containing a coordinate covalent bond are listed below.

Ammonium ion, NH4+

Hydronium ion, H3O+

Hydrogen bonding:
The electrostatic attraction between an H atom covalently bonded
to a highly electronegative atom X and a lone pair of electrons of X
in another molecule, is called Hydrogen Bonding.
CONDITIONS FOR HYDROGEN BONDING
(1) Only O, N and F which have very high electronegativity and
small atomic size, are capable of forming hydrogen bonds.
(2) Hydrogen bond is longer and much weaker than a normal
covalent bond
EXAMPLES OF HYDROGEN-BONDED COMPOUNDS

When hydrogen bonding occurs between different molecules of the

same compound as in HF, H2O and NH3, it is called Intermolecular
hydrogen bonding. If the hydrogen bonding takes place within
single molecule as in 2-nitrophenol, it is referred to as
Intramolecular hydrogen bonding. We will consider examples of
both types.
 METALLIC BONDING
The peculiar type of bonding which holds the atoms together in metal
crystal is called the Metallic Bonding.
THE ELECTRON SEA MODEL
Metal atoms are characterized by

(1) Low ionization energies which imply that the valence

electrons in metal atoms can easily be separated
(2) A number of vacant electron orbitals in their outermost shell.
For example, the magnesium atom with the electron configuration
1s2 2s2 2p6 3s2 3p0 has three vacant 3p orbitals in its outer
electron shell.
There is considerable overlapping of vacant orbitals on one atom
with similar orbitals of adjacent atoms, throughout the metal
crystal. Thus it is possible for an electron to be delocalized and
move freely in the vacant molecular orbital encompassing the
entire metal crystal. The delocalized electrons no longer belong to
individual metal atoms but rather to the crystal as a whole.
 # Explain the following:

i) H2O is liquid while H2S is a gas.

Due to the fact that the electronegativity of O-atom is higher than that of S-atom, there
is considerable H-bonding in liquid H2O molecules while the same is absent in H2S
molecule. Thus H2O molecules can associate to form a polymerized molecule (H2O)x
while H2S cannot do so. It is due to the formation of polymerized molecule, (H 2O)x
water exists as a liquid under the ordinary conditions while H2S exist as gases under the
same conditions.
ii) Ice floats on water.
or Ice has lower density than water.
Each O-atom of each H2O molecule is linked with two H-atoms of its own molecule by covalent
bonds and with two H-atoms of the neighboring H2O molecule by H-bonds. Two H-bonds are
formed between the two lone pairs of electrons present on O-atom and two H-atoms of the
neighboring H2O molecules as shown in Fig. This type of bonding between O-atom and four H-
atoms gives a tetrahedral structure to ice. We have seen that the cage-like open structure of ice
has vacant space in it. The presence of vacant space gives a large volume to a given mass of ice.
When ice is allowed to melt to come in the liquid state, some of the H-bonds in the cage-like
structure of ice are broken to some extent and water molecules come closer to each other. This
results in a decrease of volume and hence density is increased. Thus we see that liquid water
has higher density than solid ice and ice is lighter than water and hence floats on water.

Tetrahedral structure of ice (cage-like open structure)

iii) Solid NaCl does not conduct electricity whereas
molten does.
Ionic compounds do not conduct electricity when they are in the solid state.
The reason is that the cations and anions, on account of electric force of
attraction existing between them, remain tightly held together with each
other in the ionic compounds.
However, the ionic solids conduct electricity when they are in water solution
or in the fused (molten) state. The reason for this can be explained as
follows: As the temperature is raised, the kinetic energy of the ions also
increases. Ultimately when the ionic compound goes into the molten state,
the kinetic energy of the ions becomes so large that the attractive forces
acting between the ions are overcome and the well-ordered arrangement of
the ions in the ionic crystal is destroyed and consequently the ions become
free to move about in the liquid medium under the influence of the applied
electric field. Thus the ionic compounds are good conductors of electricity in
the molten state
SiCl4 is easily hydrolyzed by H2O but CCl4 is not.

Carbon does not have d-orbitals because it is found in 2 nd period. Since in

carbon tetrachloride all the valencies are satisfied so, it can not add any water
molecule by any mean.
CCl4 + H2O → No hydrolysis
Whereas in SiCl4, silicon exists in period 3, which has 3d-orbitals vacant, so it
can expand its octet so that the additional water molecule can donate a lone
pair of electron to the silicon, thus the reaction becomes
SiCl4 + 4H2O → Si(OH)4 + 4HCl

NH3 has a dipole moment but BF3 is non-polar.

BF3 has symmetrical structure in which the three B-F bonds are oriented at
an angle of 1200 to one another. The three bonds lie in one plane and the
dipole moments of these bonds cancel each other giving net dipole moment
equal to zero.
In NH3 actually have 4 attachments to the central ion: three hydrogen
and a non-bonding pair. Because of this non-bonding pair, NH3 makes
trigonal pyramidal shape and polar. The resultant dipole moment is
1.49D.

µ=0 µ = 1.49D
BOND FORMATION (VALENCE BOND THEORY)
1) According to this theory the bond formed by the overlap of
half-filled two atomic orbitals belonging to the outermost
shell of these two atoms and containing two electrons of
opposite spin is called covalent bond.
2) The overlap of two atomic orbitals gives rise to a single bond
orbital which is a localized orbital and is occupied by both the
electrons
3) As a result of overlapping there is maximum electron
density somewhere between the two atoms.
 # Explain σ and π bond.

A covalent bond which is formed by the head-to-head overlap of

the half filled atomic orbitals of the two atoms is called a σ bond.
 A covalent bond which is formed by the side to side overlap of half-
filled p-orbitals of the two atoms is called π bond.

# Distinguish between sigma and pi bond

σ-Bond π-Bond
(i) A σ-bond obtained by the head-to- (i) π-Bond is given by the side-to-side
head overlap of orbitals. overlap.
(ii) σ-Bond is a stronger bond. (ii) π-Bond is a weaker bond.

(iii) Free rotation is possible round (iii) Free rotation is not possible
the sigma bond axis. round the pi bond axis.

(iv) The probability of finding the (iv) The probability of finding the
electrons between the two nuclei is electrons between the two nuclei is
maximum. poor.
# O2 molecule formation.
# Define hybridization. Deduce the shape of BCl3 and
CH4 molecules with the help of hybridization concept.
Hybridization is the concept of mixing atomic orbitals into new
hybrid orbitals suitable for the pairing of electrons to form
chemical bonds. Hybrid orbitals are very useful in the explanation
of molecular geometry and atomic bonding properties.
Formation of three σ-bonds in BCl3 molecule which has triangular
planar shapes
For Methane
 sp3hybridization

Tetrahedral shape of CH4

# Why the bond angle in H2O is 1050 but that in NH3 is 1070
although both the central atom is sp3 hybridized?
Electronic configuration of
C(6)- 1s22s22p2
N(7)-1s22s22p3 and O(8)-1s22s22p4
The valence shell of all atoms has four electron pairs in CH4, NH3 and
H2O molecule. In CH4, four of these electron pairs are bps. In NH3,
three of these electron pairs are bps and one lp. In H2O, two of these
electron pairs are bps and two lps. Consequently in H2O molecule
there are three types of electron pair-electron pair repulsions which
are i) lp-lp repulsion ii) lp-bp repulsion and iii) bp-bp repulsion while
in NH3 molecule there are two types of repulsions which are i) lp-bp
and ii) bp-bp repulsion and CH4 has one repulsion (bp-bp).
Repulsion order-lp-lp>lp-bp>bp-bp
Due to the net effect of this difference in electron pair-electron pair
repulsions bond angle are decreasing in NH3 = 1070, H2O = 1050.
# Write a short note on Molecular Orbital Theory (MOT).
According to MOT, all the atomic orbitals of the atoms participating
in the formation of the molecule approach nearer to each other and
get mixed up to give an equivalent number of new orbitals that
now belong to the molecule as a whole. These new orbitals are
called molecular orbitals (MOs).
Molecular orbitals of a molecule are obtained by the linear
combination of atomic orbitals of the bonded atoms. The linear
combination of two AO wave functions is brought about either by
adding or by subtracting the two wave functions of two AOs. Thus
if ψ is the wave function of the MO obtained from two AOs of two
atoms A and B having ψA and ψB respectively as their wave
functions, then

The linear combination of ψA and ψB gives two MOs. One of these

is represented as ψb and the other as ψa.
BOND ORDER:
How many are the bonds in a molecule or Bond order is correctly
predicted by the Molecular Orbital theory. The number of bonds in
a molecule is one-half of the difference of the number of electrons
in the bonding molecular orbitals and the number of electrons in
the antibonding molecular orbitals. Mathematically

Information given by Bond order

The bond order as determined by the above formula is very helpful as
it gives us the following valuable information :
(1) Stability of the Molecule/Ion
A molecule/ion is stable if Nb > Na
(2) Bond Dissociation Energy
It depends upon the bond order. Greater the bond order
greater is the bond dissociation energy

(3) Bond Length

Bond order is inversely proportional to the bond
length. Higher the bond order, smaller the bond
length.

(4) Magnetic Properties

The presence of unpaired electrons in Molecular orbitals of a
species makes it paramagnetic in nature. Greater the number
of unpaired electrons, the more will be its paramagnetic
character. On the other hand, if there are no unpaired
electrons in MOs the species will be diamagnetic in nature.
# Explain hydrogen forms diatomic molecule while helium remains monoatomic.

Bond order for H2 molecule Bond order for He 2 molecule

= (nb-na)/2 = 1/2(2-0) = (2-2)/2 = 0
=1

So hydrogen forms diatomic molecule (H-H) while helium remain monoatomic.

# Draw the MO energy level diagram for O2 molecule and explain why it is
paramagnetic. Find out its bond order.

B.O. = 8-4/2 = 2
It is paramagnetic due to the presence of two unpaired electrons.
# Draw the MO energy level diagram for CO molecule and explain it’s magnetic
property. Find out its bond order.