Chemical Bonding

What is a chemical bond?

Claim: chemical bonds are what hold atoms together to
form the more complicated aggregates that we know
as molecules an extended solids .
It is more useful to regard a chemical bond as an
effect that causes certain atoms to join together to
form enduring structures that have unique physical
and chemical properties.
Most important 1: chemical bonding occurs when one or more
electrons are simultaneously attracted to two nuclei.
Most important 2: A chemical bond between two atoms forms if the
resulting arrangement of the two nuclei and their electrons has a
lower energy than the total energy of the separate atoms.
 What is a molecule?
A molecule is an aggregate of atoms that possesses
distinctive observable properties.
A more restrictive definition distinguishes between a
"true" molecule that exists as an independent particle,
and an extended solid that can only be represented by
its simplest formula.
chemical species is defined by its structure.
The structure of a molecule is specified by the identity of
its constituent atoms and the sequence in which they
are joined together, that is, by the bonding
connectivity. This, in turn, defines the bonding
geometry— the spatial relationship between the
bonded atoms. structural formulas reveal the very
different connectivity.
 Bond energy

• The amount of work that must be done to pull two

atoms completely apart; in other words, it is the
same as the depth of the “well” in the potential
energy curve. This is almost, but not quite the same
as the bond dissociation energy actually required to
break the chemical bond; the difference is the very
small zero-point energy, related to bond vibrational
frequencies.
 Potential energy curves
• The energy of a system of two atoms depends on the
distance between them. At large distances the energy
is zero, meaning “no interaction”. At distances of
several atomic diameters attractive forces dominate,
whereas at very close approaches the force is
repulsive, causing the energy to rise.
 Cause of Chemical Bonding:
• Atoms combine chemically for the following reasons:
1.Net attractive force between atoms: Atoms consist of strongly
positive nucleus and negative electrons. When two atoms come closer to
combine with each other to form a bond between them, the attractive
and repulsive forces begin to operate between them. The attractive forces
are between the electrons of one atom and the nucleus of the other atom
while the repulsive forces are between the electrons or the nuclei of the
two atoms.
• Fig. Attractive and repulsive forces operating between two atoms when they
come closer to each other.

Fig. 3.1: Attractive and repulsive forces operating between two atoms when they come closer to each other.
• When the two atoms approach closer to each other,
these forces counteract each other. The net result of
these forces may be either attraction or repulsion
between the atoms. If the attractive forces become
dominant over the repulsive forces, the net result is the
attraction between the atoms and hence they combine
together to form a chemical bond between them. On the
other hand if the repulsive forces become dominant over
the attractive forces, the atoms do not combine and
hence no chemical bond is established between them.
For example in case of hydrogen atoms, the net result is
attraction and hence two H-atoms combine together to
form H2 molecule. On the other hand in case of helium
atoms, the net result is repulsion and hence two He-
atom do not combine together to form He2 molecule.
2.Octet rule or rule of eight (Electronic Theory of Valency):
Lweis, Kossel and Longmuir (1916) tried, for the first time, to
explain why atoms combine together on the basis of the
electronic configuration of noble gases as given below.
Noble Gas At. No. Electronic Configuration
He 2 2

Ne 10 2,8

Ar 18 2,8,8

Kr 36 2,8,18,8

Xe 54 2,8,18,18,8

Rn 86 2,8,18,32,18,8
They assumed that since the atoms of noble gases do not normally
react with other atoms to form compounds, it is reasonable to
assume that the outermost shell configuration of the atoms of
noble gases is a stable configuration of 8 electrons which they
called an octet. They also concluded that the two electrons in case
of helium (called duplet) is also as stable as an octet present in
other noble gases.
The tendency of the atoms to have eight electrons in their outermost
shell is known as octet rule or rule of eight. Since helium atom has
only two electrons, this rule is called doublet rule or rule of two in
case of helium.

Octet rule was given in the form of a theory which is known as octet
theory of valency or electronic theory of valency which states that:
• In the formation of a chemical bond atoms interact with each other
by losing, gaining or sharing of electrons so as to acquire a stable
outer shell of eight electrons.
The main points of electronic theory of valency can be summarized as
follows
• Atom with 8 electrons in the outer most shell (2 in case of helium)
are chemically stable and hence are incapable of chemical
combination
• An atom having less than 8 electrons in its outermost shell is
chemically active and hence has a tendency to combine with other
atoms. The atoms possessing less than 4 electrons in their ultimate
shell usually tend to lose them, while those having more the 4
electrons in the outermost shell tend to gain the electrons during
the chemical bond formation to attain stable configuration of the
nearest inert gas.
• Atoms combine chemically as a result of transferring of electrons
from the outermost shell of one atom to that of the other or by
sharing one, two or three electron pairs between the valence shell
of both the combining atoms. The transfer of electrons or sharing of
electron pairs gives a stable configuration of 8 electrons to the
valence-shell of both the atoms.
• The tendency of an atom for transference or sharing its electron
pairs is a measure of its chemical activity.
3.Lowering of potential energy of combining atoms:
When two atoms combine together to form a bond,
there is an overall decrease in the potential energy of
the combining atoms (i.e. a system having bonded
atoms has lower energy than that having the
unbounded atoms). This implies that the bonded
atoms having lower potential energy are more stable
than that of unboned atoms having higher potential
energy.

In the process of chemical bonding between the atoms there is decrease in the
potential energy of the combining atoms and gives rise to the formation of a
system which has lower energy and hence has greater stability.
 Types of Chemical Bonds:
There are four types of bonds which hold the atoms together in a molecule:
• Ionic or Electrovalent Bond: This type of bond is established by the transfer of one or more
valence electrons from one atom to the other.
• Covalent Bond: This type of bond is established by the sharing of one two or three electron
pairs between the combining atoms. For that each of the two bonded atoms contributes one
electron to make the shared electron pair and has equal claim on the shared electron pair,
i.e. the resulting electron pair fills the outer shell of both the atoms and thus both the atoms
attain the stable configuration of the nearest inert gas.
• Co – ordinate Bond: A covalent bond in which both electrons of the shared electron pair
come from one of the two atoms is called a coordinate bond.
• Metallic Bond: It is a typical bond that is formed in metals. In this bond a variable number of
electrons are shared simultaneously by a variable number of atoms of the metal.

• All these four bonds are called strong bonds. There happens, however, attractive interactions
between the atoms which are comparatively weaker than the bonds mentioned above. These
weaker interactions are called weaker bonds. In these bonds the bonding atoms do not loss
their identity. These weaker bonds are of the following types:
• Hydrogen Bond: This bond involves the bonding of a hydrogen atom with two strongly
electronegative atoms (e. g. N, O and F) simultaneously.
• Van der walls interaction: This bond involves the interaction between atoms or molecules
having inert gas configuration.
 IONIC BOND
• This type of bond is established by transfer of an electron from one atom
to another. Let usconsider a general case when an atom A has one
electron in the valence shell and another atom B hasseven electrons. A
has one electron in excess and B has one electron short than the stable
octet.Therefore, A transfers an electron to B and in this transaction both
the atoms acquire a stable electron-octet. The resulting positive ion
(cation) and negative ion (anion) are held together by electrostatic
attraction. Fig: Illustration of the formation of ionic bond between A and
B atoms

The electrostatic attraction between the cation (+) and anion (–) produced by electron-
transfer constitutes an Ionic or Electrovalent bond. The compounds containing such a
bond are referred to as Ionic or Electrovalent Compounds.
 CONDITIONS FOR FORMATION OF IONIC BOND
The conditions favorable for the formation of an 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 7valence 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 wordsenergy must be released as a result of
the electron transfer and formation of ionic compound by thefollowing steps :
(a)The removal of electron from atom A (A – e–→A+) requires input of energy,
which is theionization energy (IE). It should be low.
(b) The addition of an electron to B (B + e–→B – ) releases energy, which is the
electron affinityof B (EA). It should be high.
(c) The electrostatic attraction between A+ and B – in the solid compound
releases energy, whichis 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), theoverall process of electron transfer and formation of ionic
compound results in a net release of energy.Therefore, ionisation of A will
occur and the ionic bond will be formed.
• Examples of three Ionic compounds (NaCl, MgO, Al2O3):
In this illustration the symbol of an element surrounded by a number
of dots (.) or crosses (x) equal to the number of valence electrons
which is also called the Lewis symbol of the element.
• The structural formula of molecules built by the union of Lewis
symbols of the component atoms are called electron dot formulas
or electron dot structures or Lewis structures.
• NaCl molecule:
Here Na (2, 8, 1) transfers its excess one electron to Cl atom (2, 8, 7)
and thus Na atom acquires the configuration of Ne (2, 8) and Cl
acquires the configuration of Ar (2, 8, 8). The electron lost by Na
atom is accepted by Cl atom and consequently Na atom is
converted into a positively charged ion (i. e. Cation) and Cl atom is
converted into a negatively charged ion (i. e. anion). The two ions
thus formed attract each other by electrostatic force of attraction
which leads to the formation of an ionic or electrovalent bond
between Na+ and Cl- ions.
Fig: Simple representation to show the
formation of NaCl ionic crystal
• MgO molecule:
In the formation of MgO molecule, Mg atom loses its two electrons from its
outer-most shell (Mg – 2, 8, 2) which are taken up by oxygen atom (O – 2,
6). This converts Mg atom into Mg2+ ion and O atom into O2- ion. The ions
thus formed attract each other and form MgO molecule.
• Al2O3 molecule:
Here Al atom has three electrons in its valence shell (2, 8, 3) and Oxygen has
six (2, 6). Two atoms of Al transfer their six electrons to three oxygen
atoms. Thus the electron octets of the Al and three O atoms are achieved.
The two Al atoms deprived of three electrons each, give two Al 3+ ions
while the three O atoms having gained two electrons each, give three O 2-
ions. In this way we get Al23+ O32- or Al2O3 molecule.
 Factors effecting the formation of ionic compounds:
The formation and the stability of the ionic compounds depend on how easily the ions consulting
the ionic compound are formed. Following are the important factors which affect the
formation of ionic compounds.
• Number of valence electrons: The atom A which is converted into cation, A+ should possess
1, 2 or 3 valence electrons while the atom B which is converted into anion, B- should have 5,
6 or 7 valence electrons. The element of groups IA, IIA and IIIA satisfy this condition for atom
A and those of groups VA, VIA and VIIA satisfy this condition for atom B.
• The ionization energy: Ionization energy of the metal atom should be low. Low ionization
energy of the metal will favor the formation of cation.
• Electron affinity: The atoms with high electron affinity will form the anions quite easily.
• Lattice energy: The lattice energy of the ionic compounds formed are high. The energy
released when one gram mole of a crystal is formed from its gaseous ions is called the lattice
energy of the crystal. Thus

A+ (g) + B- (g) A+B- (crystal) + Energy released (Latice.

Energy)
Higher the value of lattice energy of a crystal, greater will be the stability of the ionic crystal.
For the formation of stable ionic compound there must be a net lowering of the energy. For
lattice energy to have a high value, the electrostatic force of attraction between the
constituent ions of the ionic compound should be high.
• Electronegativity: Atoms A and B will form an ionic bond, if they have greatly different
electro negativities. In fact, a difference of 2 or more is necessary for the formation of an
ionic.
 Properties of Ionic Compounds:
• Physical state: Ionic compounds consist of three dimensional solid
aggregates of cation and anions which are arranged in a well-defined
geometrical pattern. Thus ionic compounds are crystal-line solids at room
temperature. They are never liquids or gases under the ordinary
conditions of temperature and pressure, since their ions lack the freedom
of movement characteristic of the liquid or gaseous state.
• Electrical conductivity: Ionic compounds do not conduct electricity when
they are in the solid state because of their crystal lattice structures.
However, the ionic solids conduct electricity when they are in water
solution or in the fused (molten) state.
Thus the ionic compounds are good conductors of electricity in the molten
state, i. e. molten ionic compounds or their aqueous solution conduct a
current when placed in an electrolytic cell.
• They are quite hard, have low volatility and high melting and boiling
points.Since in ionic solids, the cations and anions are held together very
tightly in their allotted positions by very strong electrostatic forces of
attraction, very high amount of energy (in the form heat) is required to
separate the cations and anions from one another against the force of
attraction and thus to make them free to move, as in a liquid.
Consequently the ionic solids are quite hard, have low volatility (i. e. have
low vapor pressure) and have high melting and boiling points.
 • Solubility in polar and non-polar solvents: Ionic solids are freely soluble in polar
solvents like H2O, liq. NH3 etc. On the other hand ionic solids are insoluble or
slightly soluble in non-polar solvents (organic solvents) such as C6H6, CCl4 etc.
The solubility of ionic solids in a polar solvent like water can also be explained by
saying that a water molecule is a dipole and hence the positive end of water dipole
interacts with the negative ion of the ionic solids and the negative end of the
dipole interacts with the positive ion of the same ionic crystal (as shown in Fig.
3.2)in which the dissolution of NaCl ionic crystal in water has been shown. The
interaction between the water dipoles and the ions of the crystal lowers down the
energy of the system and thus the force of attraction between the cations and
anions of the ionic solid is weakened. Consequently the water molecules tear off
the ions from the crystal lattice and make them float in the bulk of water. Further,
they are surrounded by water dipoles with the oppositely charged ends directed
towards them.

Fig. 3.2: Dissolution of NaCl (ionic crystal) in water

Explanation of dissolution on the basis of relative magnitude of lattice and hydration
energies. The dissolution of an ionic compound in a polar solvent can also be
explained on the basis of relative values of lattice and hydration energies. The
dissolution of an ionic compound in a polar solvent takes place through the
following two steps.
• Stability: Ionic crystal are very stable compounds and for
maximum stability of these crystals the oppositively
charged ions are close to one another and the similarly
charged ions are as away from one another as possible.
 • Crystal structure (Packing of ions in ionic crystals): Single ionic molecules (e. g.
Na+ Cl-) do not exist as such in the solid form of ionic compounds, i. e., ionic solids
do not exist as individual neutral independent molecules. Rather, a number of
cations and anions attraction which is non-directional and hence extends in all
directional. In order to occupy minimum space the ions arrange themselves
systematically in an alternating cation-anion pattern called crystal or lattice. Thus
we see that ionic solids consist of three dimensional solid aggregates.

Fig. 3.3: Cubical structure of NaCl ionic crystal. The bottom figure represents a cross
section of NaCl crystal.
• Ionic solids are highly brittle, i. e. if a little external force is applied on ionic
crystals, they are generally easily broken. This property is called brittleness
and can be explained as follows:
We know that ionic solids are composed of parallel layers which contain
cations and anions in alternative positions so that the opposite ions in the
various parallel layers lie over each other. When a little external force is
applied on an ionic crystal, one layer of ions slides a bit over the other
layer along a plane. The sliding of a layer over the otherresults in that the
like ions come in front of each other and hence begin to repel each other

Fig. 3.4: Explanation of high brittleness of ionic solids.

Consequently the application of a little external force brings about repulsion
between the two layers and the ionic solid breaks. Hence ionic solids are
highly brittle.
• Density: The electrostatic force of attraction existing between the
cations and anions in an ionic crystal brings these ions very close to
one another. This decreases the volume of the crystal and
consequently the ionic crystals have high density.
• They undergo ionic reactions: The reactions of an ionic compound
are precisely the reactions of its constituent ions. Such reactions
which are called ionic reactions take place as a result of collision
between cations and anions, giving rise to the formation of new
ionic compounds. Ionic reactions are practically rapid and
instantaneous (i. e. precipitation). For example Cl- ions present in
NaCl give white precipitate of AgCl as soon as AgNO3 solution is
added to that of NaCl.

• NaCl Na+ + Cl-

• AgNO3 Ag+ + NO3-
• Cl- (From NaCl) + Ag+ (From AgNO3) AgCl
(White ppt)
• They show isomorphism:Ionic solids made up of ions with identical
electronic configurations show an identity of crystalline form which is
called isomorphism. Two such pairs of isomorphs compounds are (a) NaF
and MgO and (b) CaCl2 and K2S.

•They do not exhibit isomerism: Ionic bond involving electrostatic lines of force
between opposite ions is non-rigid and non-directional. The ionic compounds
are, therefore, incapable of exhibiting stereoisomerism.
 COVALENT BOND
• The chemical bond between two atoms in which the electrons (in
pairs) are shared by both the participating atoms is called covalent
bond.
• Lewis Concept of Covalent Bond (Octet Rule of Covalent Bond):
In 1918 G.N. Lewis, an American chemist, suggested that there are atoms
which can combine with each other or with other atoms by sharing the
unpaired electrons in their outermost orbitals. Consequently the paired
electrons are shared by both the atoms and circulate about the nuclei of
both the atoms. The attractive force of the two nuclei for the shared pair
of electrons holds the atoms together and gives rise to the formation of a
bond which is called covalent bond or electron pair bond and the
compounds containing covalent bonds are called covalent compounds.

According to Lewis concept when two atoms from a covalent bond

between them, each of the atoms attains the stable configuration
of the nearest inert gas, by completing its octet (i. e. 8 electrons in
the outermost shell) or duplet (i. e. 2 electrons in case of hydrogen).
The covalent bond is established between the atoms of the same or
different elements. Since a covalent bond between atoms results by
the interaction of their electrons which become common to both
the atoms, it is also called an atomic bond.
• Types of Covalent Bond
The covalent bond formed by the sharing of one, two or three electron pairs
between the participating atoms is called single, double and triple
covalent bond respectively. Double and triple covalent bonds are called
multiple covalent bonds. these bonds are represented as follows:
Types of bond Represented by No. of electron pairs Examples
involved

Single covalent bond Single dash 1 pair = 12 H - H, Cl – Cl, H – Cl, H – O –

= 2 electrons H

Double covalent bond Double dash 2 pairs = 22 O=O

= 4 electrons

Triple covalent bond Triple dash 3 pairs = 32 NN

= 6 electrons
What is Covalency?
• The valency of an element in a covalent
compound is termed as its covalency.
Covalency of an element in a covalent compound is
equal to the number of electrons contributed by
one atom of it in the shared or linking electron
pairs. Consequently, the covalency of an element
in a covalent compound is equal to the number of
covalent bonds formed by one atom of it with the
neighboring atom. Thus the covalency of Cl in Cl2
molecule = 1, of N in N2 molecule = 3, and of C in
CH4 molecule = 4.
• Lewis formulae for covalent compounds:
• N2 molecule: The two N atoms (2, 5) each having five electrons in the
valence shell, achieve the octet by sharing three electron pairs between
them. Thus we see that both N- atoms in N2 molecule are linked by a triple
bond.
• CO2 molecule: Carbon (2, 4) has four electrons in its valence-shell. It
shares two electrons with each oxygen atom (2, 6). Thus C-atom and O-
atom both achieve their octet and carbon atom is linked with both O-
atoms by a double bond.
• Ethylene (C2H6) and acetylene (C2H2) molecule: In C2H4 each C-atom
achieves the stable octet by sharing its four electrons with C-atom
achieves the other C-atom. In this way each C-atom forms two single
bonds with two H-atoms and one double bond with the other C-atom. In
C2H2 each C-atom forms one single bond with one H-atom and one triple
bond with the other C-atom.
• F2 and HF: In F2 molecule each F atom (2, 7) has seven valence electrons.
The two F atoms achieve a stable electron octet by sharing a pair of
electrons.
In HF molecule H atom attains a doublet while F atom achieves an octet of
electrons.
Factors favoring the formation of covalent compounds:

The followings are the factors that favor the formation of covalent
compounds.
• High Ionization Energy: The atoms which have high value of ionization
energy are incapable of formation ionic bonds. They can form covalent
bonds between them.
• Equal Electron Affinities: For covalent bonding the two atoms must have
equal or almost equal attraction for electrons.
• High Nuclear Charge and Small internuclear Distance: In convalent bond
the electron charge becomes highly concentrated in the region between
the atomic nuclei. This attracts both the nuclei towards itself. This force of
attraction depends on the charge on the nuclei and the distance between
them. Hence high charge on the bonding nuclei and smaller inter nuclear
distance favor the formation of covalent bond.
• Number of Valence Electrons: Each of the two atoms should have 5, 6 or 7
valence electrons so that both the atoms achieve the stable octet by
sharing 3, 2 or 1 electron pair. The non-metals of VA, VIA and VIIA groups
respectively satisfy this condition.
• Equal electronegativity: Both atoms should have equal electronegativity
so that the transfer of electron (s) from one atom to the other may not
take place (i. e. ionic bond may not be formed). When the
electronegativity of both the atoms is equal, sharing of electron pair(s)
occurs and covalent bond is established.
 Properties of covalent compounds

• Physical State: Covalent compounds usually consist of discrete molecules and the
force of attraction between adjacent covalent molecules is weak. It is due to these
weak forces that most of the covalent compounds exist as gases or liquids of low
boiling points under the normal conditions of temperature and pressure. However,
they may exist as soft solids only when their molecular weight are high; e. g.
chlorine (mole. Wt =71) is a gas, bromine (mol. wt. = 160) is a liquid, while iodine
(mol. wt. = 264) is a solid.
• Melting and Boiling Points: With the exception of covalent solids consisting of
giant molecules (e. g. diamond, SiC AIN etc), other covalent solids have relatively
lower melting and boiling. Points than the ionic solids, e. g. boiling points of SiCl4
(covalent compound) and NaCl (ionic compound) are 58°C and 1440°C
respectively. Low boiling points are due to the fact that the attractive forces
between covalent molecules are weak van der wall’s forces.
• Solubility: With the exception of covalent solids consisting of giant molecules, all
other covalent solids are insoluble in polar solvents like H2O but are readily soluble
in non-polar solvents like C6H6, CCl4 etc. Their solubility in non-polar solvents is due
to the similarity in covalent nature of the molecules of the solute and solvent i. e.
their solubility is based on the principle: “Like dissolves like”. Covalent solids
having the giant molecules are insoluble in all the solvents. This is because of the
fact that these solids, due to their big size, are not able to interact with the solvent
molecules. Some of the covalent compounds like alcohol, amines etc. are soluble
in H2O due to hydrogen bonding.
Properties of covalent compounds
• Neither Hard nor Brittle: Covalent compounds are neither hard nor brittle.
They are soft and waxy, since they usually consist of separate molecules.
There are weak forces holding the molecules in the solid crystal lattice. A
molecule layer in the crystal easily slips relative to other adjacent layers
and there are no forces of repulsion between the layers like those ionic
compounds. Thus covalent crystals are easily broken and there is no sharp
cleavage between the layers on application of external force.
• Molecular Reactions: Covalent compounds undergo molecular reactions
in solutions, i. e. in solution covalent compounds give reactions where the
molecule as a whole undergoes a change. Since there are no strong
electrical forces to speed up the reaction between molecules, these
reactions are slow and hence need a control of temperature and pressure.
• Isomerism: Since covalent bonds are rigid and directional, they can give
rise to different arrangements of atoms in space. So, a single molecular
formula of a covalent compound may represent a number of different
compounds with different properties. This means that covalent
compounds can show isomerism. This phenomenon of isomerism is shown
mostly by organic compounds.
• Sugden’s concept of single linkages:
Sugden postulated that the central atom of the molecules like PCl5, SF6
etc. maintains its octet and in doing so the central atom is linked
with some of the combining atoms by single-electron bonds, called
singlet linkages while with the remaining atoms it is linked by the
normal two-electron covalent bonds. The singlet linkage is a special
type of bond which is formed by the one-sided sharing of only one
electron between the central atom and the combining atoms. This
bond is also called single-electron linkage, half-bond or simply
singlet.
A singlet-electron linkage is represented by a half arrow (→) with its
head pointing from the donor towards tile acceptor. On the basis of
this concept phosphorus atom in PCl5 molecule as linked with three
Cl atoms by three covalent bonds (i. e. three electron pairs are
being shared between phosphorus and three chlorine atoms) and
with each of the remaining two chlorine atoms it is linked by a
singlet linkage. Thus the structure of PCl5 is as shown below
Singlet linkage is weaker than a covalent bond and this explains
why PCl5 readily dissociates into PCl3 and Cl2.
In SF6 molecule Sulphur atom is linked with two F atoms by two
covalent bonds and with four F atoms by four singlet linkages
as shown below
• Sidgwick’s concept of maximum covalency:
According to this concept it is not necessary for an element to
have a maximum covalency of four, i. e. it is not essential
that an element be surrounded by 4 2 = 8 electrons for its
stability. The covalency of an element may exceed four and
the octet can be expanded. The maximum covalency of an
element actually depends on the period in which the
element concerned is present. For hydrogen (first period
with n=1) it is 2, for the elements of 2nd period with n=2 (Li
to F) it is 4, for the elements of 3rd (n=3) and 4th (n=4)
periods it is equal to 6 and for those in higher periods it is
equal to 8. Consequently maximum capacity of the valence
shell of an atom to have electrons (or maximum number of
electrons being shared) for the elements mentioned above
is equal to 22=4, 42=8, 62=12 and 82=16 respectively. Thus
we see that there is no anomaly in compounds like PCl5,
SF6, O5F8 etc. having central atoms making five, six and
eight covalent bonds with the combining atoms
respectively.
 CO-ORDINATE BOND
A covalent bond which is formed by the mutual sharing of
two electrons both of which are provided entirely by
one of the linked atoms (or ions) is called a co-ordinate
bond. Co-ordinate bond is also sometimes referred to
as co-ordinate covalent bond or dative bond. The pair
of shared electrons is called one pair. The atom which
furnishes the electron pair is called acceptor. A
coordinate bond is represented by an arrow which
points away from the donor to the acceptor.
• Illustration of the formation of a coordinate bond

The formation of a co-ordinate bond between two atoms, say A and B,

can be illustrated as the donor atom A has a spare lone pair of
electrons on it while the acceptor atom B is short of two electrons
than the octet in its valence-shell. A donates its lone pair B which
accepts it. Thus the two electrons of the lone pair which originally
belonged to A atom are now shared by both the atoms and this
mutual sharing of electron pair results in the formation of a co-
ordinate bond between A and B (A→B). Although the arrow head
indicates the origin of electrons, once a co-ordinate bond has been
established, it becomes quite identical with a normal covalent
bond. Both are established by a shared electron pair and have
similar properties.
• Conditions for the formation of a co-ordinate bond:
The atom acting as a donor should have a lone pair of electrons
The atom acting as an acceptor should have a vacant orbital to accept
the electron pair donated by the donor.
• Writing the electronic formula (Lewis formulae):

The compounds which contain coordinate bonds are called co-ordinate

compounds.
• H2O2 molecule:
• This molecule can be regarded as being formed by the combination of H 2O
molecule and oxygen atom. Oxygen atom of H2O molecule has two lone
pairs of electrons on it. In the formation of H2O2molecule by the
combination of H2O molecule and oxygen atom, one of the two lone pairs
on oxygen atom of H2O molecule is donated to the new oxygen atom and
thus a coordinate bond is established between oxygen atom of H 2O
molecule and the new oxygen atom.

O3 molecule:
• We know that O2 molecule is made up of two O-atoms which
are joined together by covalent bonds. As is evident from the
structure of O2 molecule, each O-atom has two unshared
pairs of electrons. When one pair of these is donated to a
third O-atom which has six electrons in its valence shell, a
coordinated bond is formed. Thus Lewis structure of O3 may
be shown as:
• Properties of Co-ordinate Compounds:
• Melting and boiling points and viscosity: A co-ordinate bond is a
combination of an ionic bond and a covalent bond. It is for this reason that
coordinate compounds have melting and boiling points, and viscosities
which are higher than those of covalent compounds but lower than those
of purely ionic compounds.
• Semi polar character: These compounds are semi-polar in character, i. e.
they are more polar than covalent compounds and less polar than the
ionic compounds.
• Physical state: These compounds are gases, liquids or solids.
• Solubility: These are usually insoluble in polar solvents like water but are
soluble in non-polar (i. e. organic) solvents.
• Conductivity: Like covalent compounds, coordinate compounds are also
non-ionic i. e. they do not conduct electric current through their aqueous
solutions or fused mass.
• Molecular reactions: Coordinate compounds are molecular and hence
undergo molecular reactions which are slow.
• Stability: Coordinate compounds are as stable as the covalent compounds.
But when they are made up of two different stable molecules (molecular
compounds), they are not very stable.
 Polar Covalent Bond
• A polar covalent bond can be define as:
A covalent bond between two dissimilar atoms which have different
electronegativity values is called a polar covalent bond.
OR
A covalent bond in which electrons are shared unequally between the linked
atoms and the linked atoms acquire fractional positive and negative
charge is called a polar covalent bond,Polar covalent bond is not a true or
purely covalent bond, since it has some polarity or ionic character. Thus it
is neither wholly covalent nor wholly ionic but has an intermediate
character.
 The molecule like HCl which have polar covalent bonds are called polar molecules. Since the
linked atoms having different electronegativity may not be the atoms of the same elements,
all covalent bonds between two dissimilar atoms are polar covalent bonds.
For example:
•H2O molecule contains two O – H covalent bonds. Since H and O atoms have different
electronegativity (H=2.1, O=3.5), both O – H covalent bonds are polar covalent bonds and H2O is
a polar molecule.
• Percentage of ionic Character in a Polar Covalent Bond:
• If two atoms A and B are linked together by a polar covalent bond,
the amount of ionic character in this bond depends, on the
difference of electronegativity values of A and B. Greater is the
difference, (XA – XB), greater is the percentage of ionic character in
A – B bond.
• Here the electronegativity of atom A (XA) has been assumed to be
higher than that of B (XB). This point can be illustrated by
considering the nature of X – H bond in halogen acids of HX type (e.
g. HF, HCl, HBr, and HI). The polarity of H – X bond in HX acids
increases with the increase of electronegativity difference, (XX – XH).
Since electronegativity of H atom remains the same throughout the
series, the polarity of H – X bond increase with the increase of
electronegativity of X atom. Thus the priority in H – X bond is in the
following order:
H – F > H – Cl > H – Br> H – I
Table:Relation between (XA – XB) values, percentage ionic character in
A – B bond and the nature of A – B bond (XA XB):
XA – XB % ionic character in A – B Nature of A – B bond and Examples of Bonds
bond its representation

0 0 Purely covalent NN, O = O, Cl – Cl, H – H

(A – B)

0.1 – 0.8 0.5 – 15 Covalent C – S, C – I, N – Cl, P – H

(A – B)

0.9 – 1.6 19 – 47 Polar Covalent Both O – H bonds in H2O

molecule are polar
covalent bonds and are
represented as O- - H+

1.7 50 50% ionic and 50%

covalent
1.8 – 2.0 55 – 63 Ionic (A- – B+) -

2.1 – 2.3 67 – 74 Ionic (A- – B+) Na – Cl

2.4 – 3.3 76 – 93 Ionic (A- – B+) Ca - F

• The following points may be noted in this regard:
When (XA – XB) = 1.7, the amount of ionic character in A – B bond
is 50% and that of covalent character is also 50%. Thus A – B
bond is 50% ionic and 50% covalent.
When (XA – XB) 1.7 (0.1 to 0.8) the amount of ionic character in
A – B bond is less than 50% and that of covalent character is
more than 50%. Thus A – B bond is predominantly covalent
and hence is represented as A – B.

When (XA – XB) 1.7, the amount of ionic character in A – B bond

is more than 50% and that of covalent character is less than
50%. Hence A – B bond is predominantly ionic and hence is
represented as A- B+.
 Dissolution of Polar molecules in polar solvents:
• When a polar molecule is dissolved in a polar solvent like H 2O, the polar
molecules of water surround the positive and negative ends of the polar
covalent compound (solute) and split it into cations and anions which are
surrounded by a definite, but unknown, number of water molecules. For
example when HCl molecule, which is a polar covalent molecule, is
dissolved in water, the polar molecules of H2O break HCl molecule into H+
and H+ ions which are surrounded by water dipoles as shown in figure
• Dipole moment(µ ):The degree of polarity of a polar covalent bond or of a
polar molecule (i. e. a molecule having a polar covalent bond) is expressed
in terms of its dipole moment (w) which is equal to the product of the
magnitude of electric charge (e) in esu and distance (d) in A° between the
positive and negative centers (i. e. bond length)

Thus
Unit of µ is known as Debye (D) [ 1 D = 10 – 10 esu A°]
 Hydrogen Bond

The attractive electrostatic force between a hydrogen atom which is already covalently
attached with a strongly electronegative atom of a molecule and another
electronegative atom of some other molecule (same molecule or different
molecule) is known as hydrogen bond.
Thus we see that in H – bond, H atom forms a bridge between two electronegative
atoms and for this reason H – bond is also called a H – bridge.
Atoms of Sulphur, phosphorus, chlorine, bromine and iodine are also highly
electronegative, but they cannot form hydrogen bond. Their incapability is due to
their larger atomic size, which result in extremely weak electrostatic field about
them.
 Properties of Hydrogen Bond
• A H – bond is a bond of hydrogen between two electronegative atoms only. It
never involves more than two atoms (excluding H – atom).
• Bond energy of H – bond is in the range of 3-10 kcal/mole while that of a normal
covalent bond is in the range of 50 – 100 kcal/mole. Thus a H – bond (i. e. H…B
bond) is muchweaker and longer than a covalent bond, A – H and hence it can be
readily ruptured. The difference in energy between A – H and H…B bonds indicates
that days have different bond lengths which, in turn show that H – atom in A –
H…B is never midway between the two atoms, A and B; rather always nearer to
atom A which is covalently bonded to H – atom. H – bond has more energy (=3-10
kcal/mole) than van der walls forces (=1 kcal/mole).
With the increase of electronegativity of the atom to which H – atom is covalently
linked the strength of H- bond also increases. Thus the strength of H – bonds in N –
H … N, O – N … O and F – H … F is in the following order.
The numbers given in brackets indicate the electronegativity values of the elements
concerned.
The strength of H – bond also depends on the size of the atom to which H – atom is
linked. For example the larger Cl and S atoms whose electro negativities are almost
the same as that of N, from H – bond to a lesser degree.
• The formation of a H – bond doesn’t involve any sharing of electron pairs. It is,
therefore, quite different from a covalent bond.
• Only O, N and F which have high electronegativity and small atomic size, are
capable of forming H – bonds.
• Hydrogen bonding results in the formation of long chains or clusters of a large
number of associated molecules like as many tiny magnets.
• Like a covalent bond, H – bond has a preferred bonding direction. This is attributed
to the fact that H – bonding occurs through p orbitals which contain the long pair
of electrons on A atom. This implies that all the three atoms in A – H …A will be in
a straight line.
 Types of Hydrogen Bond :
• Hydrogen is of two types:
• Inter – molecular Hydrogen Bond (Association): This type of H – bond
occurs between two or more molecules of the same or different
compound. Thus NHs, H80 and HP molecules are associated by inter –
molecular H – Bond.
• Intra –molecular Hydrogen bond (Chelatlon): This type of H – bond is
formed between a H – atom and an electronegative atom present in the
same molecule (intra means within). In intra molecular H – bonding, the H
– atom is bonded to two atoms of the same molecule. This type of H –
bonding may lead to the linking of two groups to form a ring structure and
such an effect is one kind of chelation. The occurrence of this type of H –
bond does not disturb the normal bond angles.
Examples of molecules showing intra – molecular hydrogen bonding are provided by o
– nitro phenol, o – hydroxy benzaldehyde, o – chlorophenol, o – hydroxy benzonic
acid (salicylic acid), o – nitro benzoic acid, maleic acid etc.
Thus we see that intra – molecular H – bonding in these molecules leads to the
formation of a six membered ring (chelation). The occurrence of H – bond of this
type is not possible in m – nitro phenol and p – nitro phenol because of the size of
the ring that would result. It is because of the non – existence of H – bond in m-
and p-isomers that would result. It is because of the non – existence of H – bond in
m –and p-isomers that o-nitro phenol has different properties from those of other
isomers. For example
• Melting point of o – nitro phenol is 214° while those of its m-and p-
isomers are 290° and 279° respectively.
• o – nitro phenol is volatile in steam and less soluble in water than the
other two isomers. p – nitro phenol shows inter – molecular H – bonding,
resulting in the association of two molecules as shown below.
 Significances of Hydrogen Bonding
Apart from providing explanation for a number of abnormal properties of certain
compounds containing H – bonding, it is also useful in explaining physiological
and geographical processes occurring around us. For example
• Physical state of water: Without H – bonding, H2O would have existed as a gas
like H2S. in that case no life would have been possible without liquid H2O.
• Structure of compounds: H – bonding is directional and on this account it
helps in studying and establishing the structure of many compounds like ice,
solid – hydrogen, fluoride, hydrates, solid acids, acid salts etc.
• Explanation of polymerization: H – bonding gives a satisfactory explanation
for the mechanism of polymerization and hence of the formation of bigger
aggregates of organic as well as inorganic molecules.
• Food materials: Molecules of most our food materials like sugars, carbo –
hydrates etc. also consist of H – bonding. For example O – atom of one OR
group of one molecule of sugar and carbohydrate is bonded with –OH group
of another molecule through H – bonding.
• Applications in geology: Many geological products such as organic compounds
contained in petroleum, coal products and complex hydrates of minerals are
formed and stablished by means of H – bonding.
• In paints and dyes: The adhesive action (i. e. stickiness) of glue, honey, dyes
and paints is also due to the presence of H – bonding in them.
 • In clothing: H – bond is of vital importance of our clothing. For example the rigidity
and tensile strength of cotton, silk or synthetic fibers are due to the H – bonding in
them.
• In biological systems: H – bonding also exists in molecules of living systems
proteins like various tissues, organs, blood, skin and bones in animals. Fibrous like
those found in hair, silk and muscles consist of long chains of a large number
(sometimes 1000 or so) of amino acids as shown below. Here R=methyl isopropyl
or butyl group.

The long chains of amino acids are coiled about one another into a spiral called helix. Such a
helix maybe either right- handed (called α- helix) or left handed (called β –helix ) as in the case
of screws.
It has been found that α- helix constitutes the more stable arrangement. N – H and C=O groups
which are vertically adjacent to one another in the helix are linked together by H – bonds. The H
– bonds link one spiral to the other (Fig. 7.32). X – ray studies have shown that on an average
there are 2-7 amino acid units for each turn of the helix(coli).
 Similarly deoxy ribonucleic acid ( DNA) has two spiral chains which are coiled about
each other on a common axis to form a double helix, 18 – 20 A° in diameter. They
are linked together between their sub – units

•Wood fibers: H – bonding also plays a significant role in making wood fibers more rigid so that
they may be used to meet the requirements of housing, furniture etc.
 Van Der Waals Forces (intermolecular Forces)

• Till now we had been dealing with the forces or bonds between atoms
leading to the formulation of molecules. These are called interatomic or
chemical forces. A Dutch scientist, J van der Waals in 1873 pointed out
that particles (atom, molecule or ions) of substances (similar or different)
exert attraction forces on each other, when they are brought near to each
other. These are physical forces (electrostatic in character) and much
weaker than chemical forces (i. e. ionic and covalent bonds). These are
named as van der Waals forces in honor of J. van der Waals who, for the
first time, used the concept of these forces to explain the deviation of
behavior of gases at low temperature from that of the ideal gases. He
proposed that particles of substances interact even if outer – shells of the
atoms have acquired the noble gas configurations:
• Van der Waals forces are very short – lived inter molecular attractive
forces which are believed to exist between all kinds of atoms, molecules
and ions when they are sufficiently close to each other.
• Unlike valence forces, van der Waals forces have nothing to do with
valence electrons of the elements. They exist in neutral molecules, ions
and atoms of inert gases or solid elements alike.
• The atoms of the molecules like N2, O2, Cl2 etc. in which the valence
orbitals are either used in normal bonding or are occupied by non-bonding
electrons, are rather firmly held together in the liquid or solid states by
van der Waals forces or bonds. These forces are almost absent when the
molecules of a gas are brought nearer to each other by increasing the
pressure and kinetic energy is withdrawn by cooling, van der Waals forces
are capable of holding the molecules together to form the liquid or solid
state. Thus a gas can be liquefied by allowing it to expand suddenly from
high pressure. During expansion the gas does work in overcoming
intermolecular forces of attraction. The energy required for this purpose is
obtained from the gas itself, thereby lowering the temperature and
causing the liquefaction.
 Types of van der Waals Forces
There are four types of van der Waals forces. The origin of each one of these has been
explained by a different scientist. The name of scientist has been associated with
that type to commemorate his contribution. The four types are
• Dipole – dipole interactions: These forces are found in polar molecules having
permanent polarity in them.

Fig. : Illustration of dipole – dipole interactions

•Ion – dipole interactions: Polar molecules are attracted toward ions. The negative end of
dipoles is attracted towards the cation while the positive end towards the anion.

Fig. 3.7: Ion – dipole interaction. (a) Cation (M+) attracts the negative end of the dipole. (b) Anion (A-) attracts the positive
end.
• Dipole – induced dipole interactions: This type of force is found in a mixture
containing polar and non-polar molecules. When a non-polar molecule is brought
near to a polar molecule, the positive end of the polar molecule attracts the
mobile electrons of non-polar molecule and thus polarity is induced in non-polar
molecule (Fig. 3.8)

Fig. 3.8: Dipole – induced dipole inter

 • Instantaneous dipole – induced dipole interactions: These forces are found in
non-polar molecules such as di-atomic gases like H2, O2, Cl2, N2 etc. as well as
mono-atomic noble gases like He, Ne, Ar etc.

Fig. 3.9: Instantaneous dipole – induced dipole interaction. (a) Nonpolar molecule with a
positive center surrounded by a symmetrical negative electron polar, (b) The displacement of
electron polar makes the non-polar molecule temporarily polar. (c) Temporarily polar molecule
polarizes the neighboring molecule and create in it the induced dipole.

In this way a large number of non-polar molecules become temporarily polar which are mutually
attracted by weak attractive forces. Since the molecules are in ceaselessly rapid motion and are
certainly departing from the site of temporary dipoles, the attractive forces acting between the
polar molecules are very week.
 Application of van der Waals Forces:
Although van der Waals forces are weak, yet they have been used to explain many
important phenomena. For example:
• It is the van der Waals forces between the molecules that cause substances like
inert gases, halogens etc. to condense to liquids and to freeze into solids, when the
temperature is considerably lowered. Thus these forces are responsible for
bringing about condensation and crystallization (at low temperatures) in the noble
gases and halogens.
• These forces account for varied hardness of certain solids. If the atoms or
molecules in any crystal are united only by van der Waals forces, the crystals can
be broken down easily. Such crystals will be soft and possess low melting points.
• These forces, though extremely week, can explain the deviation of the behavior of
gases at low temperature from that of the ideal gases.