Unit IV

Chemical Bonding

Indian Chemistry:-Philosophy of atom by Acharya Kanad:

 Maharshi Acharya kanad was a sage and philosopher from india.

 His real name was kashyap
 He was born in 600 BC in Prabhas kshetra near Dwarka in Gujrat.
 For the atomic theory, the scientist John Dalton. (1766-1844), an English chemist. and physicist
is given complete credit by western world.
 But a theory of atoms has been actually formulated by Acharya kanad about 2600 year before
Dalton.
 According to kanad a atom is smallest entity which is an indestructible (indivisible) particle
of matter

Electronic Theory of Valency:

 The electrons present in the outermost shell of an atom determine the valency of an atom and
hence called 'valency electrons.

 The electronic theory of valency was originated by Kossel and Lewis (1916) independently and
applied by Langmuir (1919).

 According to this theory, every element has a tendency to occupy inert electronic configuration
of the nearest inert gas, because it is considered as the most stable configuration (stable octet).

 If the last orbit is removed then the rest of the atom is called 'Kernel' (or core) of the atom.

 Atoms of elements containing 8 electrons in the outermost shell or orbit (or 2 electrons in case
of helium) are stable. The electronic arrangement in which 8 electrons (octet) or 2 electrons
(duplet) are present in the outermost shell of atom is known as stable configuration.

 Only those elements having less than 8 electrons in the outermost shell of their atoms are
capable of chemical combination. These elements have tendency to take part in chemical
combination in such a way so as to acquire the stable configuration of the nearest inert gas
element.

 The atoms of an element tends to achieve an octet by the smallest possible change. Therefore,
the elements having less than four valency electrons will lose (or lend) and the elements having
more than four valency will gain (or borrow) electrons to complete the octet.

 The valency of an element is the number of electrons its atom can lose or gain or share so as to
complete its octet or duplet and become stable.
Chemical Bond:

 The force of attraction which brings atoms or ions together in different chemical species is
known as ‘Chemical bond’.

 Types of chemical bonds:

1) Ionic Bond / Electrovalent Bond

2) Covalent Bond
3) Co-ordinate Bond
4) Metallic Bond
5) Hydrogen Bond

1] Ionic Bond / Electrovalent Bond:

 Such type of bond is formed by the transference of one or more electrons form one
atom to the other and consequently former becomes cation and the latter becomes
anion.

 lonic bond is called kernel bond because during formation of cation outer-most orbit is
destroyed and the remaining part in called core or kernel.

 "The number of electrons that atom of an element gains or losses to complete its last
orbit (octet) is called electrovalency".

 Nature of ionic bond is electrostatic force of attraction and it is non directional bond.

 lonic bond was introduced by Kossel.

Types of Electrovalency:

Electrovalency is of two types

1) Positive electrovalency (lonic valency) :

 The valency obtained by loss of valency electrons from the metallic atom of an element so as
to complete its last orbit (octet) is known as positive electrovalency.

 For example, Sodium atom loses 'one valency electron' to complete its octet (last shell).
Therefore, positive electrovalency of sodium atom is + 1.
 2) Negative electrovalency :

 The valency obtained by the 'gain of valency electrons' by the non-metallic atom of element,
so as to complete their last orbit (octet) is known as negative electrovalency.

 For Example, Chlorine atom gains 'one valency electron' so as to complete its last orbit.
Therefore, the negative electrovalency of chlorine is 1. In HCI formation chlorine show
valency -1 with hydrogen.

 Formation of lonic or Electrovalent Compound

The formation of ionic bond depends upon three major factors:

(i) lonization potential:

Ionization energy is the energy to remove electron from outermost orbit of an atom. The
lower the value of ionization potential, the greater will be the ease of formation of cations.

(ii) Electron affinity:

Electron affinity indicates that atom has strong tendency to accept electron, making it
easier to form an anions.The higher the electron affinity the greater is the ease of formation
of anions.
1. Formation of Sodium Chloride (NaCl) :

 A molecule of sodium chloride (NaCl) consists of one atom of sodium and one atom of chlorine.
It is formed by electrovalent linkage.

 Sodium atom (At. No. 11) has an electronic configuration (2, 8, 1) and chlorine atom (At. No.
17) has an electronic configuration (2, 8, 7).

 In the formation of sodium chloride, sodium atom loses its one valency electron and acquires a
unit positive charge (+ charge) and attains a stable configuration of nearest inert gas element
Neon (2, 8).

 The electron lossed by sodium atom is gained by chlorine atom it acquires a unit negative
charge (-charge) and attains a stable configuration of nearest inert gas element Argon (2, 8, 8).

 These two equal and oppositely charged ions (Na++ and Cl --) which are produced, unite
together by the electrostatic forces of attraction to form apparently neutral molecule of sodium
chloride (NaCl).

 Such a combination of atoms loss and gain of electrons is known as “electrovalent linkage”.

1. Formation of Magnesium oxide (MgO) :

 In a molecule of magnesium oxide one atom of magnesium combines with one atom of oxygen.

 Magnesium atom (At. No. 12) has an electronic configuration (2, 8, 2) and oxygen atom (At.
No. 8) has an electronic configuration (2, 6).
  During combination of two atoms, 2 electrons are transferred from magnesium atom to oxygen
atom. Hence by loss of 2 electrons the magnesium atom acquires + 2 charge and it attains the
stable configuration of nearest inert gas element neon.

 The 2 electrons lossed by magnesium atom are gained by oxygen atom which acquires -2 charge
and attains a stable configuration of neon gas (2, 8).

 These two equal and oppositely charged ions ( Mg++ and O-- ) are bound together with
electrostatic forces of attraction and produce neutral molecule of magnesium oxide (MgO).

 Such a union of atoms take places by loss and gain of electrons is called 'electrovalent linkage'
and the compound formed is called electrovalent compound or ionic compound.

3) Formation of Calcium Chloride (CaCl2) :

 In CaCl2 one atom of calcium combines with the two atoms of chlorine. 

 Calcium atom has electronic configuration (2, 8, 8, 2) while chlorine atom (At. No. 17) has
electronic configuration (2, 8, 7).

 In the formation of calcium chloride, calcium atom (2, 8, 8, 2) losses two valency electrons and
acquires + 2 charge and attains a stable configuration of nearest inert gas element Argon and it
forms Ca++ ions.

2] Covalent Bond:

 Definition:
A chemical bond formed by the sharing of a pair of valence electrons between two atoms of same or
different elements is called ‘covalent bond’.

 Covalent bonds constitute stable molecules, because in these bonds, participating atoms attain
a noble gas configuration after sharing of the electrons.

 Formation of covalent a bond can be visualized with the help of Lewis dot diagrams.

 Two or three pairs of electrons form a double (O2) or triple (N2) bond respectively.
Types of Covalent Bonds:

1) Formation of water molecule (H2O) :

 A water molecule is formed by combining two atoms of hydrogen with one atom of oxygen.
Each hydrogen atom (1) is in short of 1 electron to complete its duplet and oxygen atom is in
short of 2 electrons to complete its octet.

 During combination, hydrogen atoms complete their duplet by contributing one electron each
with oxygen atom and oxygen atom completes its octet by contributing two electrons with two
hydrogen atoms.

 Therefore, in water molecule, two separate single covalent bonds are formed between hydrogen
and oxygen atoms.

2) Formation of oxygen (O2) molecule :

 Oxygen molecule (O2) contains two atoms of oxygen hence it is diatomic.

 Each oxygen atom (2, 6) contains 6 valency electrons and they are in need of 2 electrons to
complete last orbit (octet).
 In the formation of oxygen molecule, each oxygen atoms shares two electrons with other
oxygen atom to complete the octet

 Hence there are two shared pairs which form double covalent bond between two oxygen atoms.

3) Formation of oxygen (N2) molecule :

 Nitrogen molecule is formed by combining two atoms of nitrogen hence it is diatomic

 Each nitrogen atom (2. 5) is in need of 3 electrons to complete its last shell (ochet). Therefore,
each nitrogen atom contributes 3 electrons for sharing.

 A molecule of nitrogen is formed by sharing three pairs of electron between two nitrogen
atoms.Thus, three shared pairs constitute a triple covalent bond.

4) Formation of oxygen (Cl2) molecule :

 In the formation of chlorine molecule one atom of chlorine combines with other atom of
chlorine.

 Each chlorine atom (2, 8, 7) contains 7 valency electrons. So it is in short of one electron to
complete the octet

 Therefore, each chlorine atom contributes one electron with other chlorine to constitute 'single
covalent bond' between two chlorine atoms

3] Co-ordinateBond:

 It is a special type of covalent bond in which the shared electrons are contributed by one atom
only; while the other atom accepts their sharing without any contribution of electrons.

 The atom which contributes electron-pair (called lone-pair) for sharing, is called the donor;
while the other atom which accept these shared electrons is called acceptor.
  The coordinate or dative bond is, generally represented by an arrow head (→), starting fromthe
donor and ending at the acceptor

1) Formation of hydronium ion (H3O+) :

 When hydrochloric acid is dissolved in water, a coordinate bond forms between water moleculeand
H+ ion.

 This reaction results in the formation of hydronium ion.

 Each water molecule forms only one coordinate bond.

2) Formation of Ammonia Borontrifluoride Complex :

 Formation of Ammonia - B orontrifluoride Complex Nitrogen atom of NH3 has one lone pair of
electrons and boron atom of BF3 has only six electrons in the valence shell. 

 Ammonia donates its lone pair of electrons to borontrifluoride molecule and forms a coordinatebond
as shown above.
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3) Co-ordinate bond between AlCl3 & Cl- Complex :
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 4] Metallic Bond:
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Definition:
Metallic bond is defined as an electrostatic force of attraction that exists between the metal ions and valence electrons.
It is a perticular type of bond that holds the atoms of metallic crystal together.

 The bonds that hold the atoms in a metal crystal together are neither ionic nor covalent in nature.

 Many theories have been proposed to explain the formation of metallic bonds. The simplest theory out of those

 is the electron sea model.


The Electron Sea Model of Metallic Bonding:

 Metal atoms have very low ionization energy which supports to the fact that their valence electrons can be
separated easily.
 Because of low ionization energy metal lose electrons & convert positive metal ions.
 The delocalized electrons no longer belongs to any individual atoms rather they belong to entire metal crystal
 This is the simplest model of metallic bonding and known as electron sea model or electron gas model.
Thus, according to the electron sea model, a metallic bond can be defined as "the electrostatic force of
attraction that the neighboring positive metallic ions have for the delocalized electrons, is known as metallic
bond”.

5] Hydrogen Bond:

Definition:
 The force of attraction between hydrogen atom of a molecule and an electronegative atom (i.e. F. O or
N) of the same or other molecule is known is Hydrogen Bond.

 Elements like nitrogen, oxygen and fluorine are the highly electronegative elements.

 When these atoms form covalent bond with less electronegative atoms such as hydrogen; the shared
pair of electrons (bond pair) shifts towards the more electronegative atom (F, N, O etc.).

 Due to this, atom of the electronegative elements (F, N, O) acquire partial negative charge (δ−)and
hydrogen atom acquires partial positive charge ( δ+)

 This hydrogen atom (with partial positive charge) attracts a more electronegative atom of the same or
other molecule and forms a bond with it. This type of force of attraction is known as hydrogen bond.

 Hydrogen bond is weaker than the electrovalent (ionic) bond and covalent bond.

 In this way, hydrogen bond behaves as a bridge between two atoms which holds one atom by covalent bond and
the other by hydrogen bonding.

 Hydrogen bond is represented by a dashed line (---) or dotted line (......) while covalent bond is represented by a
solid line (-)
1) Intermolecular Hydrogen Bond:
Intermolecular hydrogen bond forms between the hydrogen atom of one molecule and an atom of the more
electronegative elements of the different molecule.
2) Intramolecular Hydrogen Bond:
This type of hydrogen bond forms when hydrogen atom is present between two highly electronegative (F, O, N) atoms
present within the same molecule.

Effects of Hydrogen Bonding on Properties:

1. Boiling point:
Substances having intermolecular Hydrogen bonding show higher melting and boiling points: (because of large
association of molecules) in comparison to the substances do not having Hydrogen bonding

For example, B.P of CH3CH2OH is 78.5 °C while that of CH3OCH3 is -23 deg °C

2. Solubility in water:
Substances making hydrogen bonds with water show higher solubility than those who are not making hydrogen bonding.
For instance lower alcohols are highly soluble in water but alkanes are insoluble, because alkanes cannot make H-
bonding with water.

3. Physical state of matter:

Because of hydrogen bonding in water molecule, it is found in liquid state but H2S is gas. A molecule of H2S remains
free in absence of any hydrogen bonding.

 Molecular Arrangement in Solid, Liquid and Gases:

 Molecular arrangement in solid:

In solids the molecules are closely packed. They have least amount of intermolecular spaces. The force of
attraction between the molecules is very strong and free motion of molecules is not possible. That is why solids
are rigid and retain their shape.
For example: Metals

 Molecular arrangement in liquids :

In liquids the molecules are loosely packed. There are large intermolecular spaces in liquids. Theforce of attraction
between the molecules is small and motion of molecules is possible. That’s why liquids are not rigid and they
don’t have their own shape. They take the shape of the container.
For example: Water

 Molecular arrangement in gases :

In a gas the molecules are separated from one another by wide spaces. The force of attraction between the
molecules is least and the molecules have maximum freedom of motion. Hence the gas has neither a definite
shape nor a definite volume.
Gases and liquids are called fluids because of their ability to flow. For example:
Air

Solid Liquid Gases

Rigid Not rigid Not rigid

Fixed shape No fixed shape No fixed shape

Fixed volume Fixed volume No fixed volume

Classification of solid on the basis of bond type:

1) Crystalline solids:
The substances whose constituent particles (atoms, ions or molecules) are arranged in definite orderly
arrangements are called crystalline solids.
Many naturally occurring solid substances occur in the crystalline form. X-ray diffraction shown that
the regular arrangement of the constituents (atoms, ions, molecules) extends throughout three
dimensional networks.
Examples: Sodium chloride, sulphur, diamond, graphite, sugar
 Properties of crystalline solids
1) The crystalline solids exhibit regular repeating structure represented by unit cells.
2) These are characterized by long range order.
3) These solids usually show sharp melting points.
4) The crystalline solids are anisotropic. Therefore, the physical properties of crystalline solids are
different in different directions - like electrical conductivity, refractive index, thermal expansion etc.
5) When crystalline solid is cut with a sharp knife, it cleaved along perfect directions.

2) Amorphous solids:
The substances whose constituent particles are not arranged in an orderly manner are called amorphous
solids.
Examples: Plastics, rubber, starch, proteins, glass, coal, coke etc.

Properties of amorphous solids.

1) The amorphous solids do not have regular arrangement of particles but are randomly arranged
in three dimensions.
2) They do not have specific long range order.
3) They do not have sharp melting points.
4) The amorphous solids are isotropic. Therefore their physical properties are same in alldirections.
5) When an amorphous solid is cut with a sharp knife, it results in an irregular breakage.

Differences between crystalline solids and amorphous solids:

Sr. Crystalline solids Amorphous solids

No.
1 They have definite arrangement of atoms, They have random arrangement of atoms,
ions or molecules. ions or molecules.
2 They have sharp melting points. They do not have sharp melting points.
3 They have definite geometry. They do not have definite geometry.
4 They are anisotropic. They are isotropic.
5 Cleavage is uniform. Cleavage is not uniform.
6 Examples: Sodium chloride, diamond, Examples: Glass, rubber, plastic.
graphite , etc.
Properties of metallic solids:

The properties of metallic solids can be explained on the basis of electron sea models as follows:
1) Metallic lustre: The bright lustre of metal is due to presence of delocalised mobile electrons.
When a beam of light falls on the metallic surface, the loosely held electrons absorb photons
of light and start oscillating to and fro at a frequency equal to that of incident light. The
oscillating electrons emit electromagnetic energy in the form of light. As a result, the incident
light appears to be reflected from metal surface and the surface exhibits shining appearance.

2) Electrical conductivity:
The electrical conductivity of a metal is due the presence of mobile valence electrons. When a potential
difference is applied across the metal, the free mobile electrons move readily towards positive electrode.
These electrons simultaneously replaced by the electrons coming from the negative electrode. This
constitutes electrical conductivity.

Fig. 4.13
 2) Thermal conductivity:
The thermal conductivity of metal is due to the presence of high valency electrons. When the metal is
heated, the kinetic energy of electrons in that region increases. As the electrons in metallic crystal are
free and mobile, these energetic electrons move rapidly to the cooler parts and some of their thermal
energy is transferred to these parts by means of collision.
Therefore, the heat is transferred from hotter to cooler parts of metal.

Fig.4.14

4) Malleability and ductility:

In the metal the valency electrons are spread all over the crystal due to this the metallic bond is non-
directional. Whenever any stress or force is applied on metal, the position of positive metallic kernals
is changed without destroying the crystal. Due to slippage of one layer of kernels relative to adjacent
layers of kernals the metallic lattice get deformed. The deforming forces simply move the kernals from
one lattice site to another. The nearest neighbors can thus be changed easily and new metal bonds can
be formed readily, explains the malleability (beaten into sheets) and ductility (drawn into wires).

Fig.4.15
5) Tensile strength or tenacity:
Tensile strength is the ability of metal to resist pull without breaking. Metals have high tenacity because
there is a high electrostatic force of attraction between the positively charged kernals and sea of
electrons.
 6) Elasticity in metals:
Elasticity is the property of metal by virtue of which metal can regain its original shape as soon as the
stretching force is released. In the metallic crystal elasticity is due to the ease with which positive
kernals in metallic lattice can slide from one site to another.
7) Hardness:
Hardness is the property of metal by virtue of which metal can resist wear or abrasion and
penetration. The hardness is due to the strength of metallic bond. The strength of bond based ontwo
factors;
i) Number of valence electrons: Greater the number of valence electrons stronger is the
metallic bond.
ii) Size of kernel: Smaller the size of kernel of metal atom, strong attraction of mobile electrons
and therefore stronger is the metallic bond.

 Unit cell :
Unit cell is the smallest individual group of atoms or ions or molecules in a crystalline solid which repeat itself in
three dimentions and constitutes the entire crystal lattice.

Parameters of Unit cell.

The unit cell is characterized by
i) Its lengths along three edges a, b and c.
ii) The angles α, β, γ. between the pairs of edges

1) Simple Cubic unit cell (SC)

In this type of unit cell, constituent particles (atoms, ions, molecules) are present only at the corners of the unit
cell. Simple Cubic unit cell consist of total eight atoms at the corner of cube.
The atoms present at the corner of a unit cell are shared by eight another unit cells.
Therefore,each atom contributes 1/8 to the unit cell. Hence in Simple cubic unit cell, number of atoms per
= (8  1/8) = 1 atom.

2) Body Centred Cubic unit cell (BCC)

In this type of unit cell, atoms are present at the corners of cube i.e eight atoms at corner and oneat the center of
the unit cell.

Fig. 4.21
i) Eight atoms of the corners = 8 x 1/8 = 1 atom.
ii) Atoms at the body centre = 1 atom.
Hence in Body centered cubic unit cell, number of atoms per unit cell
= 1 + 1 = 2 atoms.

3) Face Centred Cubic unit cell (FCC)

In this type of unit cell, atoms are present at the corners i. e eight atoms at corner and at thecenter of each
face i.e six atoms at the center of six faces of the unit cell.
 i) Eight atoms of the corners = 8 x 1/8 = 1 atom.
ii) Atoms at each of the six face centres = (6 x 1/2) = 3 atoms.
Hence in Face centered cubic unit cell, number of atoms per cubic unit cell = 1 + 3 = 4 atoms.
 1. Hexagonal close pack (HCP) crystal:
Unit parameters of unit cell of this crystal are. a= b ≠ c.
The spheres are packed in such a way that the spheres in every second row are placed in the depressions or
interstices between the spheres of the first row sphere. Each sphere or atom has six closest neighbours.

Further extending the packing in third row, the spheres will be vertically aligned with spheres inthe first row.
This gives rise to hexagonal close packing (hcp).

If the spheres of first layer are labelled as A and the spheres of second layer are labelled as B. Then the
third layer is also labelled as A. Hence in hcp, the pattern is ABABAB ...... is called hexagonal close packing or
hcp. Each atom in an hcp is surrounded by 12 nearest neighbours, sixare in the planar hexagonal layer B and six
(three in layer A above and three in layer A below) form trigonal prism around the central atom.
Hence the coordination number of hexagonal close packing crystal is 12.
For example:: Co, Mg, Zn.
Number of Atoms per HCP Unit Cell:
1. Corner Atoms:
12 corners × (shared by 6 cells) = 2 atoms.

2. Face Atoms:
2 faces × (shared by 2 cells) = 1 atom.

3. Middle-Layer Atoms:
Fully within the cell = 3 atoms.

Total Atoms = 2+1+3 = 6