Bonding and Structure

NCUK -Chemistry Department Page:1
Topic C
Bonding and Structure
➔ Ionic and covalent bonding.
➔ Duet Rule and Octet Rule in terms of stabilising atoms.

➔ How the position of elements in the periodic table will determine the type of
bonding when the elements are in a compound.
➔ The nature of ionic bonding, ionic lattice packing, and basic properties of ionic
compounds. Lewis structures.
➔ The nature of covalent bonding. Basic properties of non-polar and polar

covalent compounds. Lewis structures.
➔ Electronegativity as predictor of (i) and (ii), and polarity of the bond. Pauling’s
electronegativity scale.
➔ The electron sea model of metallic bonding. Properties of metallic bonds.

➔ Dative covalent bonding; electron donors and acceptors. Simple Lewis
structures (e.g ammonium ion, hydronium ion, Al2Cl6).
➔ The nature of van der Waals intermolecular forces. Examples of compounds.

Properties arising from bond strength.
➔ The nature of dipole-dipole intermolecular forces. Examples of compounds.

Properties arising from bond strength.
➔ The nature of hydrogen bonds. Atoms that form hydrogen bonds. Bond type
and strength to explain boiling point trends across the period (e.g. in CH4, NH3,
H2O and HF) and down the group (e.g. HF, HCl, HBr and HI).
➔ Comparison of intermolecular bond strengths and properties within

compounds.
➔ Valance Shell Electron Repulsion Theory to explain and help draw molecular
shapes using dashes and wedges.
➔ Describe the solid state structures of giant covalent macromolecules including

diamond, graphite and graphene and silicon (IV) oxide (silicon dioxide).
Kings International School Yangon, Myanmar

SLOs
C1 - Understand the formation of ions in terms of electron loss or gain and how the valency
of an atom and its position in the periodic table affects the type of bonding it is involved
in.
C2 – Explain that ionic bonding is an electrostatic attraction between oppositely charged ions
which form a giant lattice, e.g., NaCl.
C3 - Draw “Dot and Cross” (Lewis) structures to explain ionic bonds in compounds.
C4 – Explain the concept of metallic bonding and relate this to the ph ysical and mechanical
properties of metals.
C5 – Explain that a covalent bond is strong electrostatic attraction between the nuclei of two
atoms and the shared pair of electrons between them.
C6 – Understand the formation of dative bonds in terms of donation of lone pairs of

electrons.
C7 – Draw “Dot and Cross” (Lewis) structures to show electrons in covalent molecules
including, single and double bonds, and species that exhibit dative covalent bonds.
C8 – Explain the concept of electronegativity.

C9 – Describe the polarity of a covalent bond in terms of the electronegativity differences of
the bonded atoms and use partial charges to show the polarity of a bond.
C10 –Perform simple calculations to distinguish between covalent and ionic bonds using
Pauling’s electronegativity scale.
C11 – Explain how the physical properties of a compound, including solubility, melting point,
boiling point and conductivity are related to its structure and bonding.
C12 – Understand the difference between intermolecular and intramolecular bonding.
C13 – Describe dipolar forces in terms of asymmetry of electron distribution and van der
Waals forces in terms of polarisability and molecular weight.
C14 – Describe the interactions in molecules such as NH3, H2O and HF that lead to the
formation of hydrogen-bonds.
C15 – Outline the importance of hydrogen bonding to the physical properties of substances.
C16 – Examine bond type and strength to explain the boiling point trends across the period
(eg CH4, NH3, H2O and HF) and down the group (eg HF, HCl, HBr and HI).
C17 – Describe, interpret and/or predict the effect of different types of intramolecular or
intermolecular bonding on the physical properties of substances.

C18 – Explain and predict the shapes of and bond angles in some simple molecules in terms
of repulsion of electrons around the nucleus, with ability to account for and include
lone pairs in this description.
C19 – Draw using wedges and dashes linear, v-shaped, trigonal planar, trigonal pyramidal,
tetrahedral, trigonal bipyramidal and octahedral shaped molecules.
C20 – Compare and contrast the macromolecular structures of carbon species (graphite,
diamond and graphene) and correlate their physical properties (melting point/boiling
point, conductivity, mechanical and lubricating properties) to their structures.
C21 – Describe the bonding in silica (silicon dioxide) and relate this to its physical properties.

Almost all atoms combine with other atoms except noble gases or “o” group/18th group
elements; due to their un-reactivity, they are called inert gases (also noble gases). In this
process, the atom either gains, loses, or sometimes shares the electrons.
When elements form compounds, they either lose, gain, or share electrons so as to achieve
stable (low-energy) electron configurations similar to the next higher or lower noble gas in the
periodic table. This simple idea forms the basis of the electronic theory of bonding.
In 1916, Kossel and Lewis put forward their ideas of chemical bonding and suggested that the
atoms of different elements combine with each other in order to complete their 8 electrons in
their outermost shell (called an octet) or 2 electrons in their outermost shell (called a duplet).
since these configurations are stable configurations of inert gases and noble gases (group 18).
Because of their low energy configurations, they are the least reactive elements.
Atoms combine in order to complete their 8 electrons (octet) so as to acquire a stable inert gas
configuration. This can occur in two ways.
1. By sharing of electrons. This can occur in two ways, as follows:

(a) When the shared electrons are contributed equally by the two combining atoms, the
bond formed is called a covalent bond.
(b) When shared electrons are contributed entirely by one of the atoms but shared by
both, the bond formed is known as a coordinate bond, also called a dative bond.
2. By the complete transference of one or more electrons from one atom to another atom.
The number of electrons that an atom loses or gains while forming an ionic bond is called
its electrovalency, and the chemical bond formed is termed as “electrovalent bond” or
“ionic bond.”
NOTE :
In the formation of a molecule, only one outer shell electron is involved, and they are known as
valence electrons. The inner shell electrons are well protected and are generally not involved in
the combination process. It is therefore quite reasonable to consider the outer shell electrons, i.e.,
valence shell electrons, while discussing the chemical bonds.
The Lewis Structure

G. N. Lewis introduced simple symbols to denote the valence shell electrons in an atom. The
outer shell electrons are shown as dot (•) or cross () surrounding the symbol of an atom.
These symbols ignore the inner shell electrons. Examples are:
• •
Li • , • C • , • N •
• ••

The number of dots or cross around the symbol gives the number of electrons present in the
outermost shell. This number of electrons helps to calculate the common valency of the
element. That is why these electrons are called valence shell electrons.
NOTE :
The common valency of the element is either equal to the number of dots in the Lewis symbol
(if these are  4) or 8 minus the number of dots (if these are > 4).
For example, Li, Be, B and C have valencies 1,2,3, and 4 respectively, i.e., equal to the number
of dots, whereas valencies of N, O, F and Ne are 3, 2, 1, and 0 respectively, i.e., 8 minus
number of dots.
Exception to octet and duplet rule In the formation of the compounds like BeCl2, BF3,
AlCl3, etc., the central atom (Be, B or Al) has less than 8 electrons, i.e., these are electron-
deficient compounds.
Cℓ  Be  Cℓ  , F•x B x• F , Cℓ •x Aℓ x • Cℓ
x• x•
F Cℓ
On the other hand in the formation of compounds like PCℓ3, SF6, IF7 etc., the central atom (P, S,
I)
has more than 8 electrons as shown below.
Cℓ F F
F F F Fn
x
Cℓ
x
P x  Cℓ S I
F F F F
x
Cℓ Cℓ F F F
10 electrons around P 12 electrons around S 14 electrons around I (iodine)
Chemical Bond A chemical bond is a type of force of attraction which holds the
various atoms/ions/molecules together.
There are five three ways of forming chemical bonds between atoms.
1. Covalent bonding
2. Ionic bonding
3. Metallic Bonding
Aside from these three chemical bonds, other bonds are also formed by dipole-dipole
interaction; however, these are not considered to be true chemical bonds.

4. van der Waal’s forces

5. Hydrogen Bonding
1. Covalent Bonds A covalent bonding is a type of force of attraction which binds

atoms of same or different elements by mutual sharing of electrons.
Characteristics of Covalent bonds

(i) Covalent bonds are formed between atoms of non-metals as a result of the attraction
between the nuclei of two atoms.
(ii) Covalent bond can form between atoms of the same elements (e.g., H2, Cl2) or atoms of
different elements.
(iii) The atoms involved in covalent bond formation contribute equal number of valence
shell electrons for sharing. The number of electrons an atom uses to form bonds is
called its valency. For example, carbon uses 4 electrons to form bonds, so its valency is
four.
(iv) The shared pair of electrons between two similar or dissimilar atoms of non –metal
elements are also known as a bond pair of electrons. These are the electrons that are
actually taking part in bond formation.
(v) The valence electrons not involved in sharing are known as “lone pairs” or “bond pairs”
of electrons.
(vi) When the atoms share one electron pair, the bond is called a single covalent bond and
shown as — line.
When atoms share two electron pairs, the bond formed is called a double covalent bond
and shown as line.
Similarly, when atoms share three electron pairs, the bond is called a triple covalent
bond and shown as line.
(vii) In a simple way of showing a covalent bond, only outer shell electrons are shown:
In order to show covalent bonding between two atoms a cross (×) and a dot (•) diagram
is used.
The sign cross (×) is used to represent the electrons of one atom, while sign dot (•) is
used to represent the electrons of another atom.
(viii) Most of the covalent compounds exist in liquid or gaseous form; they are poor
conductors of electricity in the fused or dissolved state.
(ix) Covalent compounds are usually insoluble in water and iother polar solvents. However,
these are more soluble in non-polar solvents.
Examples of Covalent bonds
1. Covalent bond in hydrogen molecule.

x
H + x H H H
H atom H atom or
H–H
H2 molecule
2. Covalent bond in chlorine molecule.
xx xx
xx xx
x
x x Cl x x x x x Cl x x x
Cl +x x x x Cl x x x
xx xx
x
xx xx
Cl2 molecule
A simple way of showing covalent bond is by showing only the outer shell electrons.
xx
x
Cl Cl x
x or Cl – Cl
xx
3. Covalent bond in oxygen (O2)

xx xx
x
O + xx O x
x O x O x
x
O=O
O2 molecules
Can also be shown as
Xx xx
O + xx O O xx O
xx xx
x x
4. Covalent bond in nitrogen (N2)

x
x
x x x
N + x N x N N x
x
x
N≡N
5. Covalent bond in HCl

xx xx
x x x
H + x x H x
Cl Cl
xx xx
H – Cl
6. Covalent bond in H2O
xx xx
x
H + xx O x +
x H H O x
x
x
H
O
H H
7. Covalent bond in CH4
+ H
x x
H
x x
H + x C x + H H C H │
or H—C—H
x x
+ H │
H
H
8. Covalent bond in C2H4

H x H H H
x
x
C C or
x C=C
x x
H H
H H
The electrostatic force of attraction between the nuclei and a shared pair of electrons is
called a covalent bond. Chemical bonding, of any type, is a force of attraction, and the
cause of attraction should be explained while defining the bonding.
Modern Concept of Covalent Bond According to modern theory of chemical bonding,

atoms combine with each other to minimize their energy. Using the H2 molecule as an
example, it is found experimentally that to dissociate 1 mole of the molecules into atoms,
433kJof energy is required (absorbed).
H2(g) + 433kJ H(g) + H(g)
Conversely, in the formation of 1 mole of the molecule from hydrogen atom, 433 kJ of energy
is released, i.e.,
H(g) + H(g) H2 (g) + 433kJ

When two atoms come closer to each other, new forces come into operation. These forces are
of two types.
(i) The forces of repulsion between the nuclei of these reacting atoms and between the
electrons of these atoms. These forces tend to increase the energy of the system.
(ii) The forces of attraction between the nucleus of one atom and the electrons of the other
atom. These forces tend to decrease the energy of the system.
eA
New forces of attraction
HA HB
New forces of repulsion
New forces of attraction
eB
INFINITE DISTANCE
NO INTERACTION

COME CLOSER
INTERACTION STARTS

 No interactions at large distances.  Interactions starts as the atoms come closer

The attractive forces tend to bring the two atoms close to each other, whereas the repulsive
forces tend to push them apart. It has been found that in the beginning, the magnitude of
attractive force is greater than the repulsive forces. Therefore, the atoms go on approaching
each other, and potential energy of the system continues to decrease. Ultimately, a state is
reached where attractive forces just balance the repulsive forces. This state is reached when
atoms are at critical distance r0. At the distance greater than r0 the attractive forces are
dominant, whereas at a distance smaller than r0, the repulsive forces are dominant. The
maximum lowering of energy takes place at critical distance r0.

In this situation, the two hydrogen atoms are said to be bonded together to form a stable
system, i.e., a molecule.
Energy
Inter nuclear distance

0
Isolated H atoms
r0 Approaching
H atoms
Bonded H atoms
r0
r0 = Bond length
Orbital concept of Covalent Bond According to this concept,
A covalent bond is formed by the partial overlap of two half -filled orbitals containing electrons
of opposite spins.
H Atom H- Atom
H2 Molecule
1s Orbital 1s Orbital
Overlapping takes place –Covalent bond is
formed

OR
The “partial overlap” means that a part of the electron cloud in each of the two half-filled
atomic orbitals becomes common. As a result, the probability of finding electrons in the region
of overlap is much higher than at other places. Thus, two electrons (with opposite spins) keep
on exchanging position between the two atoms but are present for maximum time in the
region of overlap and hence are attracted to both the nuclei simultaneously thereby forming a
bond between the two atoms.
NOTE 
 In fact, after the overlap, the two atomic orbitals merge into each other resulting into the
formation of a new orbital called molecular orbital ( MO) .
Same way, the formation of H⎯F molecule is explained as below:

In case of formation of hydrogen fluoride molecule, when one atom of fluorine (1s2, 2s2, 2px2 ,
2py2, 2pz1) having one unpaired electron in its p- orbital comes closer to hydrogen atom with
electron opposite spin in its 1s- orbital, then two half-filled orbitals overlap each other and a
chemical bond is formed between the two atoms. This is shown as follows,
Formation of H-F molecule

In the formation of the F2 molecule, one atom of fluorine (1s2, 2s2, 2px2, 2py2, 2pz1) approaches
another atom of fluorine having the electron of opposite spin in the 2pz orbital. The half-filled
orbitals overlap each other, resulting in the formation of a fluorine molecule as shown below.

 The orbital concept can explain why only H2 exists and He2, H3, H4, and other elements
do not. A helium atom contains a fully filled atomic orbital (1s2), which cannot overlap with
the 1s orbital of another helium atom because only half-filled atomic orbitals can overlap with
each other. Thus, He2 is not formed.
Further, after the formation of the H2 molecule, no more half-filled atomic orbital is available,
and so no more bond can be formed. Therefore, H3 and H4 cannot be formed.
Bond energy or Bond dissociation energy

The energy required to break one mole of bonds of the same kind is known as "bond energy"
or "bond dissociation energy."
Factors affecting bond energy 

(i) Size of the atoms  Greater is the size of the atoms, greater is the bond length, and less is
the bond dissociation energy, i.e., less is the bond strength.
(ii) Multiplicity of bond  The stronger the bond between the same two atoms, the greater
the bond dissociation energy. This is due to two factors: first, atoms become closer together,
and second, the number of bonds to be broken increases.
(iii) Number of lone pairs of electrons present Greater the number of lone pairs of electrons
present on the bonded atoms, greater the repulsion between the atoms and hence less is the
bond dissociation energy.
For example, for a few single bonds, we have
Bond energy
Bond Lone pairs of electrons
(kJ/mol)
C− C 0 348
N− N 1 163
O− O 2 146
F− F 3 139

Bond length
“It is the average distance between the centres of the nuclei of two bonded atoms.
Bond length is expressed in terms of Angstrom ( 1A0 = 10¯10 m). It is determined

experimentally by X-ray diffraction methods.
Factors affecting bond length 

(i) Size of the atoms  The bond length increases with increase in size.
(ii) Multiplicity of bond The bond length decreases with the multiplicity of the bond. Thus,
the bond length of carbon-carbon bonds are in the order
C≡C < C= C < C− C

(iii) Type of hybridization Because an s-orbital is smaller in size, the s-character increases,
resulting in a shorter hybrid orbital and thus a shorter bond length.
For example,
sp3, C−H > sp2, C−H > sp, C−H
Bond Angle
We know that a bond is formed by the overlap of atomic orbitals. The direction of overlap
gives the direction of the bond in covalent species.
"The angle between the lines representing the direction of the bonds, i.e., the orbitals
containing the bonding electrons, is called the bond angle."
OR
A bond angle is the angle between any two bonds that include a common atom, usually
measured in degrees.
For example, H− C− H bond angle in CH4, H−N−H bond angle in NH3, H− O −H bond angle in
H2O.

Electronegativity
"The electronegativity of an element is the tendency of its atom to attract the shared pair of
electrons towards itself in a covalent bond."
Electronegativity differs from electronic affinity, ionization energy, etc. Because these relate to
atoms in their isolated state, whereas electronegativity is a property of an atom in its bonded
state.
Let us consider two atoms that are not identical, e.g., hydrogen and chlorine, which form the
covalent compound HCl. Since the electronegativity of chlorine is greater than that of
hydrogen, the former attracts a shared pair of electrons more than the latter. So the chlorine
end of the molecule becomes slightly negative, and the hydrogen end becomes slightly
positive.
H + ⎯ Cl ¯
The value of electronegativity of various elements increases on moving left to right across
the period in the periodic table.
 Fluorine (F) is most electronegative element, after fluorine, next most electronegative
atom is oxygen (O), followed by chlorine (Cl). Nitrogen has the same electronegativity as
chlorine.
Polar & Non-Polar Covalent Bonds

1. Non-Polar Covalent Bond  If two similar atoms come close to each other and form a
bond by sharing their electrons, the shared electrons are equally attracted by the two atoms
as there is no difference in electronegativity between the participating atoms. In other words,
the shared electrons are not displaced toward any one atom. Hence, no polarity is developed.
This leads to the formation of a completely non-polar bond.
NOTE 
The important characteristic of a non-polar bond is that the electron cloud is completely
symmetrical and there is no charge separation at all.
The examples of some non-polar molecules are Cl2, O2, N2 etc.

H  H or OR
Exactly H⎯H
in the centre
Non polar covalent bond between H-atoms
2. Polar Covalent Bond  When two dissimilar atoms having different electronegativities
combine together to form a covalent bond, the shared electron pair does not lie at equal
distances from the nuclei of both the bonded atoms but shifts towards the atom having
greater electronegativity. Since more electronegative atoms attract the electrons more
strongly, the distribution of electrons gets distorted, i.e., the electron cloud is displaced more
towards the more electronegative atom. As a result, one end of the molecule, having more
electronegative atoms, becomes slightly negatively charged while the other end acquires a
slightly positive charge. Thus, positive and negative poles are developed, and this type of
bond is called a polar covalent bond (or a covalent bond with partial ionic character).
For example, in the case of the hydrogen chloride molecule, the chlorine atom is more
electronegative than the hydrogen atom. So, the force of attraction exerted by chlorine on the
shared pair is greater than that exerted by hydrogen. Hence it will be shifted towards
chlorine, i.e., the electron density of the electron cloud is more concentrated on the chlorine
side than on the hydrogen side. Consequently, chlorine becomes slightly negatively charged
and hydrogen becomes slightly positively charged.

H x Cl or
or H+ ⎯ Cl  ¯
More attracted
towards Cl
Polar covalent bonds in HCl
The examples of some polar molecules are BrCl , H− F, ICl, H−I, etc.

NOTE 
It may be noted that in the case of symmetrical molecules like CO2, CCl4, etc., although there
are a number of polar bonds present, the molecule on the whole is non-polar. This is due to
the fact that the polar bonds cancel each other out.
Coordinate- Covalent Bond or Dative Bond / Semi Polar Covalent Bond

It is a special case of a covalent bond. It is formed by the mutual sharing of electrons between
the two atoms, but the shared pair of electrons is contributed only by one of the two atoms,
the other atom simply participates in sharing.
The atom that donates an electron pair for sharing is called the donor, and it must have
already completed its octet. On the other hand, the atom that accepts the electron pair in
order to complete its octet is called an acceptor.
The coordinate –covalent bond is represented by an arrow ( ) pointing from donor

towards the acceptor.
Let us consider the formation of the ozone molecule. A molecule of oxygen contains two
oxygen atoms, which share four electrons and complete their octets. Now, if an atom of
oxygen having six valence electrons comes close to an oxygen molecule, it shares a lone pair of
electrons with one of the oxygen atoms of the molecule. It can be represented as shown
below:
Some other examples of coordinate covalent bonds/ Dative bonds are as below:
1. Formation of H2O2
.. ..
H : O: H H: O: H H OH
.. .. or
+  :O
.. : H
:O:
..

2. Formation of 𝑵𝑯+
𝟒
H H H + H +
HN 
 + H+  H N+ H or HN H or H N H
H H H H
3. Formation of SO2
  

 O 


 S 
 + O


 or O=S O
4. Formation of HNO3
 
H× O ×N Xx O





  or H O N=O
O O
5. Formation of CO

x x
x C x

 O or C = O

2. Ionic bonding Ionic bond is formed by the transference of one or more electrons
from one atom to another atom.
Oppositely charged particles attract each other. This attractive force is often referred to as
an electrostatic attraction. An ionic bond is the electrostatic electrostatic attraction that holds
ions together in an ionic compound. The strength of the ionic bond is directly dependent on
the quantity of the charges and inversely dependent on the distance between the charged
particles. A cation with a 2+ charge will make a stronger ionic bond than a cation with a 1+
charge. A larger ion makes a weaker ionic bond because of the greater distance between its
electrons and the nucleus of the oppositely charged ion.
The cations and anions orient themselves in a 3D crystal lattice in such a way that attractive
interactions maximize and the repulsive interactions minimize. Ionic bonds are usually weaker
than metallic bonds but stronger there the other types of bonds.
Characteristics of Ionic Bonds
1. An Ionic bond is formed between a metal and a non-metal atom.
The metallic atom loses its valence electrons and changes into a positive ion (cation),
while the non-metal atom gains electrons and gets converted into a negative ion
(anion).
2. The oppositely charged ions are held together by electrostatic force of attraction. This
electrostatic force of attraction is called ionic bond.
3. The number of electrons that an atom loses or gains while forming an ionic bond is
called its valency. This valency is equal to the charge on the ion.
For example, in NaCl, the valency of Na is +1 and the valency of Cl is -1.
4. Ionic compounds usually exist in the form of crystalline solids.
5. Ionic compounds generally have high melting and boiling points, and are soluble in
water.
6. Ionic compounds do not conduct electricity in the solid state, but they conduct
electricity in molten form or when dissolved in water.
7. There are some metals that can form more than one ion in compounds. These metals
are called transition metals. For example, iron can form Fe2+ and Fe3+ ions in
compounds.
8. Some ionic compounds, such as Al2O3 and MgO, have such a high melting point that are
used as refractories, i.e., heat resistant materials, to line the insides of high temperature
furnace, to make crucibles, spark plug for motor cars, etc. They are used so because
they have high melting points.
For example:
MgO melting point 2800 °C
Al2O3 melting point 2000 °C (used in spark plug and crucible)
Examples of Ionic Bonds:
1. Ionic Bond in Sodium Chloride

Na (11) : 2, 8, 1
Cl (17) : 2, 8, 7

–
xx + xx
xx xx
x x Cl x x x x x Cl x x x
Na + x x x x Na x x x x
xx xx
-
xx Na ion xx
Cl- ion
OR + xx −
xx
Na + x Cl xx [Na]+ [ x Cl xx ]-
xx xx
2. Ionic Bond in Magnesium Oxide

Mg (12): 2, 8, 2
O (8) : 2, 6
2+ 2–
xx xx
M + x O x xx M x O x xx
g g
xx xx
or
xx
Mg + x [Mg]2+ [O]2–
O x
xx

Solid magnesium oxide
6. Ionic Bond in Calcium Chloride

Ca (20): 2, 8, 8, 2
Cl (17): 2, 8, 7
xx xx
xx xx
x x x Cl x x x + Ca x x Cl x x x
x x x + x x x x
xx xx
xx xx
– 2+ –
xx xx
xx x
x x x Cl x x x Ca x x Cl x x x
x x x x x x x
xx xx
xx xx
Cl- Ca2+ Cl-
Chloride ion Calcium ion Chloride ion
xx xx
Mg +2 x x [Ca]2+ 2[ x Cl xx ]–
xClx x or
xx
xx xx
[ xx Cl x ]– [Ca]2+ [ x Cl xx ]–
xx xx
Unit cell of Calcium chloride

Unit Cells
The structure of a crystalline solid, whether a metal or not, is best described by considering its
simplest repeating unit, which is referred to as its unit cell. The unit cell consists of lattice
points that represent the locations of atoms or ions. The entire structure then consists of this
unit cell repeating in three dimensions, as illustrated below.
A unit cell shows the locations of lattice points repeating in all directions.
A crystal lattice structure and unit cells with the most straightforward structure and the most
basic unit cell. To visualize this, imagine taking a large number of identical spheres, such as
tennis balls, and arranging them uniformly in a container. The simplest way to do this would
be to make layers in which the spheres in one layer are directly above those in the layer
below, as illustrated below.
This arrangement is called simple cubic structure, and the unit cell is called the simple cubic
unit cell or primitive cubic unit cell.
When metal atoms are arranged with spheres in one layer directly above or below spheres in
another layer, the lattice structure is called simple cubic. Note that the spheres are in contact.
A simple cubic lattice unit cell contains one-eighth of an atom at each of its eight corners, so it
contains one atom total.

2D and 3D representations of ionic compounds

1. Sodium Chloride
OR
Sodium chloride lattice structure
2. Magnesium Oxide
OR

OR
Magnesium oxide lattice structure
IONIC BOND AS AN EXTREME CASE OF POLAR COVALENT BOND

We know that when two dissimilar atoms having different electronegativities combine
together to form a covalent bond, the shared electron pair does not lie at equal distances from
the nuclei of both bonded atoms but shifts towards the atom having greater electronegativity.
Thus, one end of the molecule, having a more electronegative atom, becomes slightly
negatively charged while the other end acquires a slightly positive charge.
What is electronegativity?
Definition
Electronegativity is a measure of the tendency of an atom to attract a bonding pair of
electrons.
The Pauling scale is the most commonly used. Fluorine (the most electronegative
element) is assigned a value of 4.0, and values range down to Caesium and Francium
which are the least electronegative at 0.7
In cases where the electronegativity difference between the two atoms bonded by a covalent
bond is very high, an electron can be completely transferred to a highly electronegative atom,
and the less electronegative atom loses its hold on its own electron, thus losing it to the more
electronegative atom. This results in the formation of oppositely charged ions, which are
bonded due to electrostatic forces of attraction. This type of linkage between the atoms is an
electrovalent or ionic bond.
For example, in lithium fluoride (LiF), F has the highest electronegativity, which is very large as
compared to lithium. The electronegativity difference between the two atoms (lithium and
fluorine) is so high that the fluorine atom may be in complete possession of shared paired
electrons. It may be considered as if an electron had been lost by converting Li to F in lithium
fluoride. This causes an ionic bond to form between lithium and fluorine atoms (Li+ F¯).
Partial Ionic Character If two atoms in a covalent molecule is linked together and have
different electronegativity, the bond formed is polar. In other words, the bond is said to
possess partial ionic character.

The extent of partial ionic character is determined by the difference in electronegativities of

the combining atoms. More the difference in electronegativities, greater will be the ionic
character.
(i) If the electronegativity difference between the two atoms is 1.9, the bond is said to have
50% ionic character and 50% covalent character.
(ii) If the electronegativity difference between the two atoms is more than 1.9, the partial
ionic character of the bond is more than 50% and the bond is taken as ionic.
(iii) If the electonegativity difference between the two atoms is less than 1.9, the bond is
predominately covalent.
Predicting whether a Compound is Ionic or Covalent using Pauling’s

electronegativity scale:
Electronegativity: Electronegativity is a measure of the tendency of an atom to attract an
electron to form a bond. The electronegativity difference two atoms ∆EN in a compound use
to determine whether a compound is ionic or covalent.
If ∆EN < 0.4, then its pure covalent bond.
If 0.4 <∆EN <1.8, then its polar covalent bond.
If ∆EN > 1.8, then it’s an ionic bond.
A simple method to calculate the percentage ionic character of a covalent bond is based on
the measurement of the dipole moment.
Dipole Moment In a polar molecule, there are two poles present in the molecule.
Hence, the molecule is said to possess an electric dipole. Further, since the molecule as a
whole is electrically neutral, the negative charge is always equal in magnitude to the positive
charge.
“The product of the magnitude of a negative or positive charge (q) and the distance between
the centres of positive and negative charges is called the dipole moment.”
The dipole moment is usually denoted by .. Mathematically it is expressed as,
 = q d
The charge ‘q’ is of the order of 10¯10 e.s.u., and the internuclear distance ‘d’ is of the order of
10¯8 cm, therefore, the dipole moment ‘’ is of the order of 10¯10  10¯8 = 10¯18 e.s.u. cm. This
quantity is known as one Debye and is denoted by the symbol D. Thus,
D = 1 10¯18 e.s.u. cm.
Dipole moment and molecular structure
(i) Diatomic molecules  A dipole moment is a vector quantity, i.e., it has magnitude as well
as direction. It is often represented by an arrow with its tail at the positive centre and head
pointing towards the negative end.
(+ −)

As a polar diatomic molecule possesses only one polar bond, the dipole moment of that
molecule is equal to the dipole moment of that polar bond, e.g., in case of HCl, the molecular
dipole moment of HCl bond is 1.03 D. Thus,
H+ Cl  ¯ =1.03 D
 The greater the electronegativity difference between the bonded atoms, the greater the
dipole moment. For example, dipole moments of hydrogen halides are in the order:
H⎯F > H⎯Cl > H⎯Br > H⎯I
(ii) Polyatomic molecules  As a polyatomic molecule has more than one polar bond, the
dipole moment is equal to the resultant dipole moment of all the individual bonds (called
bond moments). The magnitude of this resultant dipole moment not only depends upon the
values of the individual dipole moments of the bonds but also on their arrangement in space.
Applications of the dipole moment:

1. In determining the polarity of bonds
2. In determining the symmetry (or shape) of the molecule
1. In determining the polarity of bonds The greater the magnitude of the dipole moment,
the higher the polarity of the bond. It is important to note that this concept is applicable to
molecules containing only one polar bond. In the case of a non-polar molecule like H2, O2,
N2, etc., the dipole moment is found to be zero. This is because there is no charge separation
in these molecules.
2. In determining the symmetry (or shape) of the molecules  The dipole moment is an
important factor in determining the shape of molecules containing three or more atoms. For
instance, if any molecule possesses two or more polar bonds, it will not be symmetrical if it
possesses some molecular dipole moment, as in the case of water (m =1.84D) and ammonia
(m =1.49 D).
 But if a molecule contains a number of similar atoms linked to the central atom and the
overall dipole moment of the molecule is found to be zero, this will imply that the molecule is
symmetrical, i.e., in these molecules, the centres of positive charge exactly coincide with the
centres of negative charge. These molecules do not show any attraction in an external
electrostatic field.
1. Boron Trifluoride (BF3)
BF3 has zero dipole moment even though B and F have different electronegativities and
each of B-F bond is polar and has the same dipole moment. This is because, in the
molecules of BF3, the fluorine atoms lie at the vertices of an equilateral triangle while
boron atom lies at its centre. As a result, the individual dipole moments give a net sum
of zero.

Net dipole moment zero ( =0)
2. Methane molecule (CH4)

The methane molecule has zero dipole moment because the individual dipole moments
cannel out due to the molecule's symmetrical tetrahedral shape.
3. Methane molecule (CCl4)

The carbon tetrachloride molecule has zero dipole moment because the individual
dipole moments cannel out due to the molecule's symmetrical tetrahedral shape.
4. Carbon dioxide molecule (CO2)

In the carbon dioxide molecule, there are two polar bonds. These polar bonds possess
the same value of dipole moment, but the overall dipole moment of the molecule is
found to be zero. Individual dipole moments in this molecule are of equal magnitude,
but their directions are opposite to each other and hence cancel out.

𝜹− 𝜹+ 𝜹−
5. Nitrogen trifluoride (NF3) and ammonia (NH3)

Both NH3 and NF3 molecules have a pyramidal shape with one lone pair of electrons on
the N atom. As fluorine is highly electronegative, it appears that the N-F bond should be
more polar, and the net dipole moment of NF3 should be much greater than that of NH3.
NOTE 
The N− F bond is more polar than N− H bond but orbital dipole due to lone pair is in the
opposite direction as the resultant dipole moment of N − F bonds due to this reason NF3
has less dipole moment than NH3.
The dipole formed between the lone pair and nitrogen atom has to be taken into
consideration, which is in the direction of the lone pair.
F is more electronegative than nitrogen; therefore direction of the bond is from
nitrogen to fluorine, whereas nitrogen is more electronegative than hydrogen, and the
direction of the bond is from hydrogen to nitrogen.
The resultant moment of the N-H bond adds up to the lone pair's bone moment,
whereas the resultant moment of the three N-F bonds partially cancels the resultant of
the lone pair. Hence the net dipole moment of NF3 is less than that of NH3.
6. Water molecule (H2O)

Dipole moment of water is 1.84 D which is equal to the resultant dipole moment of two
O-H bonds.
OR

3. Metallic bonding
About three-fourths of all the known elements are metals. Metals have characteristic
properties such as high electrical and thermal conductivity, ductility, malleability, high tensile
strength, etc. The metal atoms cannot be bonded by an ionic bond because such a bond
cannot be formed between similar atoms. They cannot form covalent bonds since covalent
bonds are formed only for non-metal atoms.
In metals the atoms are packed together very closely in an orderly arrangement. This is shown
in the following figures.
Arrangement of atoms in a metal

Different theories have been put forward to explain the bonding in metals, but the most
simple theory has been proposed by Lorentz and is known as the electron gas or electron sea
model.
Electron gas or electron sea model ➢ According to this theory, metals have low ionization
energy because their valence electrons are held very loosely, i.e., they are almost like free
electrons. A metal atom is supposed to consist of two parts: the valence electron and the
remaining part (the nucleus and inner shells), which is called the kernel. These positive ions, or
kernels, are held in three-dimensional space in a definite pattern in the sea of mobile electrons.
This model is called the "electro-gas model" because the electrons are free to move in all
directions like the molecules of a gas.
These free electrons are shared between the atoms. Each atom gives up some electrons to
become a positive ion. These electrons go into the spaces between the ions as shown below:

It’s like the positively charged ions of the metal are surrounded by a "sea of electrons." The
attraction between the positive and negative charges holds the structure together. We call this
metallic bonding.
Free electrons
Or delocalised electrons
Positive ions
Bonding in metals
Metallic bonding is the force of attraction between the negative electrons and the positive
metal ions.
The metal ions are big and cannot move. The electrons are very small and can move freely
throughout the metal. Metals are described as consisting of positive ions in a “sea of
electrons.” Metals conduct electricity because the electrons can move freely. They conduct
electricity both when solid and when molten.
Metallic bonds are very strong. But they are weaker than ionic bonds.
So metals have very high melting points. Most metals have high melting points.
Covalent bonds vs Ionic Bonds
A covalent bond is generally stronger than an ionic bond. This is well illustrated by
the extremely high melting and boiling points of covalently bonded network solids
like diamond, silica, SiC, etc., where all the bonds are covalent bonds.
Moreover, there is no such thing as a pure ionic bond (each ionic bond has some
covalent character), and the only pure covalent bonds are those between two atoms
of the same element in the molecules of elementary substances.
The ionic bond is not as strong as a covalent bond because
The covalent bond is made up of the sharing of electrons. There is an atomic orbital
overlap between two bond-forming atoms, and a sigma bond is formed. Because the
bond length is short, the attractive force has a greater influence and the atoms
become closer together. Single and double bonds are weaker than triple bonds and
require high energy to cleave the bond.

Metallic bonding and physical and mechanical properties
The strong attraction between atoms in metallic bonds makes metals strong and gives them a
high density, high melting point, high boiling point, and low volatility.
The mechanical properties of metals, such as strength, ductility, malleability, toughness, and
hardness, depend on the number of valence shell electrons. Group II metals are harder, have
a higher melting point, and have a higher boiling point than group I metals because their
metallic bonding is stronger due to the presence of two outer shell electrons.
Ions Containing More Than One Atom

Some ions contain more than one atom.
For example, sulphate ion (SO42–), hydroxide ion (OH–), carbonate ion (CO32-), ammonium ion
(NH4 +), etc. In these groups of atoms, the charge is not on a particular atom but is spread over
all atoms.
Molecular Substances
Most non-metallic elements like H2, O2, F2, Cl2, Br2, etc. have molecular substances. These
elements consist of small covalent molecules. Not only these elements but even most covalent
compounds like CO2, H2O, SO2, CH4, etc. consist of molecular structures.
In their structure, small covalent molecules are bonded with weak intermolecular forces,
which break easily. Due to these weak intermolecular forces, their boiling points and melting
points are low, and many of them exist in a liquid or gaseous state.
van der Waal’s forces These are interparticle forces among the non-polar molecules
such as neon (Ne), hydrogen (H2), oxygen (O2), fluorine (F2), bromine (Br2), chlorine (Cl2), etc.,
in gaseous, liquid, or solid states. The existence of such forces was first of all given by the
Dutch chemist van der Waal, and they are known after his name as van der Waal’s forces .
Origin of van der Waal’s forces ➔ In order to understand the origin of van der Waal’s forces,
let us consider a monatomic molecule of neon. Each neon atom has its own electron cloud
symmetrically distributed around the nucleus. It can be imagined that due to the rapid
movement of electrons, the electron distribution of the atom may become unsymmetrical
with a slight increase in electron density on one side. This would be the separation of positive
and negative ends at a particular instant. In other words, the molecule develops a temporary
dipole. Such an atom having a small temporary dipole is called an instantaneous dipole. This
instantaneous dipole influences the electron distribution of the other molecules in the vicinity
and induces a dipole in them also. The attractive forces between the instantaneous dipoles
and induced dipoles are called van der Waal’s forces. These are then attracted to each other
exactly in the same way as the permanent dipole.
Hence, it goes on increasing from fluorine to iodine. As a result of this, F2 and Cl2 are gases
at room temperature; Br2 is liquid, whereas I2 is solid.

• Because of increasing van der Waals forces of attraction between the molecules as we
go down the group, the melting and boiling points increase while the volatility
decreases with the increase in atomic number from fluorine to iodine.
Instantaneous dipole due Symmetrical distribution of electron cloud

to motion of electrons
Instantaneous dipole Instantaneous induced dipole
Origin of van der waal’s forces
The halogens exist as diatomic molecules. Since these molecules are nonpolar, they will only
exhibit weak London dispersion forces. London dispersion forces are actually caused by
instantaneous and random distortions in a molecule's electron cloud.
In halogens, these distortions (London dispersion forces) of electron clouds in the molecular
orbitals (MO) get instantaneously distributed in such a way that one region has a higher
electron density and another with a lower electron density. This creates induced dipoles or
intermolecular forces between two halogen molecules.
+
F2 _
_ F2 𝛿+ 𝛿−
+
+
F2 _
- F2
+
+ F2
_
Weak dipole-dipole attraction (van der Waals forces)

The dipole- dipole interaction arises due to electrostatic interactions between the oppositely
charged ends of temporary dipoles.
Now, as you go down the halogen group, the size of the atoms, and implicitly the size of their
electron clouds, increases. It means these instantaneous distortions in the electron
distribution due to an increase in size will create more powerful temporary dipoles.
Uses of molecular substances

1. Many of these are often used in perfumes and flavourings since their molecules
evaporate easily to give a smell.
2. Small amounts of some molecular substances are put in soap and toothpastes to give a
pleasant smell.
3. These molecular substances are also used to provide artificial flavours in sweets, soft
drinks and ice creams.
4. They are also used in insect repellents, room deodorants.
5. Some of them are used as electrical insulators in transformers and circuit breakers since
they do not conduct electricity.
Properties of molecular substances

1. Most molecular substances are insoluble in water.
2. Molecular substances are soluble in organic solvents like carbon tetrachloride,
chloroform, petrol, ethanol etc.
3. Molecular substances do not conduct electricity in any physical state because they do
not contain ions and their electrons remain in fixed positions around individual atoms.
The macromolecules
Diamond and Silica
The macromolecular structure is found in the cases of silicon, diamond, and silicon dioxide
(SiO2), as well as in polymers.
Each carbon atom in a diamond is tetrahedrally joined to four other carbon atoms. These four
carbon atoms are tetrahedrally joined to other carbon atoms, and this process is repeated
over and over again.

Diamond
Silica, is an oxide of silicon with the chemical formula SiO2, found in nature as quartz and in
various living organisms. The silicon dioxide, a molecule which is not really a molecule, at
least when it is found in nature, as it forms a giant covalent structure rather than a simple
covalent structure. Silicon dioxide or silica is one of the hardest and most common materials in
the Earth's crust. In case of SiO2, each silicon atom is bonded to four oxygen atoms, and each
oxygen atom is directly in touch with two silicon atoms.
Silica, an oxide of silicon with the chemical formula SiO2, is found in nature as quartz and in
various living organisms. The silicon dioxide molecule is not really a molecule, at least when it
is found in nature, as it forms a giant covalent structure rather than a simple covalent
structure. Silicon dioxide, or silica, is one of the hardest and most common materials in the
Earth's crust. In the case of SiO2, each silicon atom is bonded to four oxygen atoms, and each
oxygen atom is directly in touch with two silicon atoms.
So the better way is to write (SiO₂)n, so that you do not forget that SiO₂ does not exist in the
isolated form (monomeric form), but is a polymer having a large network of O and Si atoms
bonded together.
The π bond between Si and O is quite weak, so it does not prefer π bonding (double bond).
To maximize their orbital overlap, Silicon makes 4 sigma bonds with Oxygen.
OR

Physical properties of Silica

Due to the tetrahedral structure, the melting point of silicon dioxide is very high. The strong
silicon-oxygen covalent bonds get broken at very high temperatures, close to 1700 oC. Also,
silicon dioxide is very hard and rigid, and this is again due to the strong covalent bond between
silicon and oxygen. Due to the absence of free electrons within the molecular structure, silicon
dioxide is a very bad conductor of electricity, and acts as an insulator. Silicon dioxide is
insoluble in water and in all organic solvents. However, it is soluble in alkalies and hydrofluoric
acid.
Graphite
Graphite is a half-metal and a type of crystal carbon, as well as one of the most well-known
carbon allotropes.
Graphite is composed of layers of carbon atoms that are arranged in 6-membered hexagonal
rings. These rings are attached to one another on their edges. In fact, each carbon atom is
bonded into its layer by three strong covalent bonds, leaving each atom with a spare electron
that, when combined, forms a delocalized sea of electrons that loosely bonds the layers
together.
The forces between the layers of graphite are weak. This means that the layers can slide over
each other. This makes graphite slippery, so it is useful as a lubricant.
Graphite
Graphene
Graphene is a single layer of carbon atoms arranged in a hexagonal lattice structure, forming a
two-dimensional (2D) material with exceptional mechanical, electrical, and thermal properties.
It is widely studied for its potential use in various fields such as electronics, energy storage,
and biomedicine

Graphene is a nanomaterial arranged in a two-dimensional layer of carbon atoms with sp2

hybridization that are connected in a hexagonal lattice structure.
Carbon nanotubes or Graphene nanotubes, or single wall carbon nanotubes, are graphene
sheets rolled into a tube
Properties and uses of macromolecules
1. Macromolecules have high melting and boiling points. They do not conduct electricity
and are insoluble in water. Silicon dioxide (SiO2) is used as thermal and electrical
insulation.
2. Diamond is the hardest substance known, used for cutting tools, jewellery, etc. Crystals
of quartz (SiO2) are used in timepieces because of its accuracy of vibration controls the
clock time and also makes them very accurate.
3. The strong covalent bonds make these substances quite hard, so they are used as
abrasives.
For example, powdered silicon dioxide is a mild abrasive used in toothpaste.

Ceramics
There is one type of solids called ceramics. There is no clear definition for ceramics.
These ceramics are formed at a very high temperature but their shapes are created at room
temperature before the heating.
There are two types of ceramics:
1. Natural ceramics → stone and rocks
2. Man made ceramics → mud bricks hardened by fire, all types of pottery,
China cups and plates.
Properties of Ceramics
1. Ceramics are also heat resistant materials which have high melting point used as
refractories.
2. Ceramics are resistant to corrosion and chemicals, the ceramics crucibles are used in
industry to hold molten metals.
3. They are used in insulating big electrical cables, since they are good electrical insulators.
4. Ceramics are usually brittle i.e. they break into pieces when given a hard blow.
HYDROGEN BONDING
Hydrogen bonding refers to the formation of Hydrogen bonds, which are a special class of
attractive intermolecular forces that arise due to the dipole-dipole interaction between a
hydrogen atom that is bonded to a highly electronegative atom and another highly
electronegative atom which lies in the vicinity of the hydrogen atom.
Definition ➢
Whenever a molecule contains a hydrogen atom linked to a highly electronegative atom (like
F, O, or N), this atom attracts the shared pair of electrons more, and so this end of the
molecule becomes slightly negative while the other end (i.e.-end) becomes slightly positive.
The negative end of one molecule attracts the positive end of the other, and as a result, a
weak bond is formed between them. This bond is called the hydrogen bond. It is represented
by dotted lines, as shown below:
H δ¯ Xδ+ Hδ¯ Xδ+ Hδ Xδ+
Thus, as a result of hydrogen bonding, a H- atom links the two electronegative atom
simultaneously, one atom links the two electronegative atoms simultaneously one by covalent
bond and the other by a hydrogen bond. Hence, it is said to form a hydrogen bridge.
Hydrogen bonding is weaker than an ionic bond or a covalent bond but stronger than van der
Waals forces. Hydrogen bonds can exist between atoms in different molecules or in parts of
the same molecule.
Conditions for hydrogen bonding

In the formation of hydrogen bond, the following conditions must be fulfilled:
1. The molecule must contain a highly electronegative atom (like F, O, N) linked to H-atom.
The higher the electronegativity, more is the polarization of molecule.
2. The size of the electronegative atom should be small. The smaller the size, the greater is the
electrostatic attraction.
Thus, only F, O, and N atoms can form hydrogen bonds, as these atoms are small in size and
have electronegativities.
 Chlorine having same electronegativity as that of nitrogen does not form hydrogen
bond due to its large size.
3. The electronegative atom must have an unshared pair of electrons. For example, in oxygen
atom in H2O contains two unshared pairs of electrons, while nitrogen atom in NH3 contains
only one unshared pair of electrons. Fluorine atom in H − F contains three unshared pairs of
electrons.
Examples of hydrogen bonding

1. Formation of hydrogen fluoride (HF)
In HF each molecule has one hydrogen atom which can form a hydrogen bond, and there
are three lone pairs of electrons on the fluorine atom. The total number of hydrogen bonds
is limited by the number of hydrogen atoms and on average each HF molecule will be
involved in two hydrogen bonds.
When two hydrogen fluoride molecules interact with each other then, they form a zig-zag
structure involving interaction between positively charged hydrogen of one molecule with
negatively charged fluoride of another molecule.
2. Formation of water (H2O)

In H2O each molecule has two hydrogen atoms and two lone pairs of electrons on the
oxygen atom. This means that there can be many more hydrogen bonds formed between
water molecules than between HF molecules. Each water molecule can potentially be
involved in up to four hydrogen bonds. In fact, water has the optimum number of H atoms
and lone pairs to form an extensive network of hydrogen bonds.

OR
Hydrogen bonding in water molecule
3. Formation of water (NH3)
Ammonia is a pungent-smelling colorless gas that can be condensed into a liquid under cold
temperatures and pressure. It is made of one atom of nitrogen bonded with three atoms of
hydrogen and is denoted by the formula NH3.
It is a commercially important compound and is also a common nitrogenous waste. It is

produced naturally as well as through human activities. Ammonia can be hazardous in
concentrated form. It is readily soluble in water.
In contrast to the case of water, with two stable hydrogen bonds per oxygen atom of water
molecule, liquid ammonia shows a weaker hydrogen bonding network with only one
hydrogen bond per nitrogen atom of each molecule
4. Alcohols (ROH) & carboxylic acid (RCOOH)

OR
The alcohols have higher boiling points than corresponding alkyl halides, ethers, or
hydrocarbons is because, for the molecules to vaporize, additional energy is required to
break the hydrogen bonds. Alternatively, association through hydrogen bonds may be
regarded as effectively raising the molecular weight, thereby reducing volatility
Intramolecular Hydrogen Bonding in ethanoic acid
Each ethanoic acid molecule has one O—H bond but is capable of forming double hydrogen
bonded dimers as shown in the diagram below. In a pure carboxylic acid two molecules are
bonded together using two hydrogen bonds to produce a dimer. A dimer consists of two
identical molecules bonded together.
Ethanoic acid dimerisation
The dimer formed due to the hydrogen bonds doubles the size of the molecule, thereby
increasing van der Waal’s intermolecular forces. This results in carboxylic acids having higher
boiling points when compared to other organic compounds of similar carbon numbers or
molecular masses.
Due to this dimerisation the experimental molecular weight of acetic acid is double the
theoretical molecular weight of acetic acid.
NOTE 
When ethanoic acid is added to water, the carboxylic acids do not form dimers. Rather,
hydrogen bonds are formed between the individual molecules of the acid and water molecules.
It is because of these interactions that carboxylic acids can dissolve in water to form acidic
solutions.

The carboxylic acids with low molar mass up to four carbon atoms are freely soluble in
water. As the chain length of the carboxylic acids increases the solubility in water decreases
rapidly.
Intramolecular Hydrogen Bonding in ortho nitrophenol

It is formed when hydrogen atom is in between the two highly electronegative (F, O, N) atoms
present within the same molecule. For example, in o-nitrophenol the hydrogen is in between
the two oxygen atoms
Intramolecular hydrogen bonding in o-nitro phenol
The main difference between intermolecular and intramolecular forces is that intermolecular
forces exist between the molecules themselves, whereas intramolecular forces exist
between atoms within a molecule.
Effects of hydrogen bonding

Hydrogen bonding helps in explaining the abnormal physical properties in several cases.
1. H2O is a liquid whereas H2S, H2Se and H2Te are all gases at ordinary temperature. The
reason for this is that the case of water, hydrogen bonding causes association of the H2O

molecules, with the result that the boiling point of water is more than that of other
compounds. On the other hand, there is no such hydrogen bonding in H2S, H2Se, and H2Te.
2. NH3 has higher boiling point than PH3. This is again because there is hydrogen bonding in
NH3 but not in PH3.
3. Ethanol ( C2H5OH) has higher boiling point than diethyl ether ( C2H5OC2H5) or diethyl amine
(C2H5)2NH because there is hydrogen bonding in ethanol but no hydrogen bonding in the later.
4. Carboxylic acids (ethanoic acid, CH3COOH) shows relative molecular mass (Mr) twice, i.e.,
120 in benzene because of dimmer formation. The actual relative molecular mass of ethanoic
acid is 60.
NOTE 
 It is important to note that when ethanoic acid molecules are dissolved in water, they are
more likely to form H-bonds with water molecules than with themselves, so dimers do not
form. That is the reason why ethanoic acid, being an organic compound, is soluble in water
because of H-bond formation with water molecules.
5. The physical state of H − F is in liquid form while physical states of other halogen acids like
H − Cl, H − Br, H −I are in gaseous form. This is due to strong hydrogen bonding in H − F
molecules (average two H−bond per H − F molecule. Although fluorine atom in H − F contains
three unshared pairs of electrons but has only one H atom therefore, it is only able to form
two H−bond per H − F molecule). This results the liquid state of H − F because of more
aggregation of the molecules, while other halogen acids are not be able to form hydrogen
bonds.
Question: Why ammonia exists in gaseous form (although it contains three N−H bonds)
while H2O exists in liquid form?
Answer
The oxygen atom in H2O contains two unshared pairs of electrons, while nitrogen atom in NH3
contains only one unshared pair of electrons. As a result, water forms four hydrogen bonds
per H2O molecule as compared to NH3, which forms only one H-bonds per NH3 molecule. This
more extensive H-bonding in H2O leads the higher boiling point of water.
Question: How many H − F bonds are there in one H − F molecule? Also write the maximum
number of H− bonds per H − F molecules?
Answer: In one H − F molecule only one H − F bond is present. Although fluorine atom
contains three unshared paired of electrons but it is able to form only two H−bond per H − F
molecule.
This results the liquid state of H − F. But the boiling point of H − F is less than that of H2O since
in water there is more intense hydrogen bonding i.e., two hydrogen bonds per H2O molecule.

6. Ice has lower density than that of water. In case of solid ice, the hydrogen bonding give rise
cage like structure of water molecule. As a matter of fact, each water molecule is linked
tetrahedrally to four water molecules as shown below. In it each oxygen atom is tetrahedrally
surrounded by four oxygen atoms. This gives rise to an open cage like structure with strong
covalent bonds (shown by solid lines) and Hydrogen bonds.
Cage like structure of H2O in ice

Each H2O molecule linked to four H2O molecules tetrahedrally.
The ice has stronger hydrogen bonds on average than liquid water.
The extra hydrogen bonds that occur when water freezes increase the space between
molecules, causing a decrease in overall density. In fact, each water ice molecule
forms hydrogen bonds with four other molecules, while water molecules only form
hydrogen bonds with an average of 3.4 other molecules.
Obviously, the molecules are not as closely packed as they are in the liquid state. When the ice
melts, this cage-like structure collapses, and the molecules come closer to each other. Thus,
for the same mass of water, the volume decreases and the density increase. As a result, at
273K, ice has a lower density than water. That is why ice floats on water.
Explanation of the maximum density of water at 277 K (40 C). At 273K (00C), there is sufficient
hydrogen bonding present in the water molecules (or ice). As a result, an open cage-like
structure with a larger volume and thus a low density exists.
On heating, the hydrogen bonds start collapsing and the molecules start coming together,
resulting in a decrease in volume and an increase in density. This goes on up to 277 K (4 0 C).
After 277K, the increase in volume due to the expansion of the liquid water becomes greater
than the decrease in volume due to the breaking of H-bonds. Thus, after 277 K, there is a net
increase in volume due to heating, which means a decrease in density. As a result, the
maximum density of water is 277K.
Intermolecular bonding Intramolecular bonding

▪ Intramolecular forces ae the chemical ▪ Intermolecular forces are the electrostatic

bonds holding the atoms together in interactions between the molecule.
the molecule. ▪ The intermolecular forces are usually much
▪ Three major types of chemical bonds weaker than the intramolecular forces, but
are the metallic bond, the ionic bond, still, they play important role in
and the covalent bond. determining the properties of the
compounds.
▪ The major intermolecular forces include
dipole-dipole interaction, hydrogen
bonding.
SLOs: C11
How physical properties of a compound including solubility, melting point, boiling

point and conductivity are related to its structure?
Chemical bonds are the electrical forces of attraction that hold atoms or ions together to form
molecules. Different types of chemical bonds and their varying intensities are directly
responsible for some of the physical properties of minerals, such as hardness, melting and
boiling points, solubility, and conductivity. Chemical bonds also influence such other
properties as crystal symmetry and cleavage.
Stronger bonds between atoms make them more difficult to separate, and, in general,
stronger chemical bonds result in greater hardness, higher melting and boiling points, and
smaller coefficients of expansion. There are four principal types of chemical bonds found in
minerals: ionic, covalent, metallic, and van der Waals forces.
An ionic bond is the result of the electrostatic attraction between two oppositely charged ions.
Ionic bonds exist because some elements tend to capture or lose one or more electrons,
resulting in a net positive or negative charge. These are called ions. An ion that bears a positive
charge is a cation. An ion with a negative charge is an anion. Ions may carry a single charge,
such as Na+ and Cl−, or may have multiple charges, such as Ca2+ or Fe3+. Oppositely charged
ions tend to attract one another because the cation can transfer electrons to the anion,
allowing each ion to achieve better stability. For example, Na+ and Cl− readily combine to form
NaCl, halite (salt). Most minerals are held together by some form of ionic bond. Ionic
compounds do not conduct electricity in a solid state, but rather in a dissolved state due to the
free movement of ions.

In order for an ionically bonded solid to melt, some of the bonds, but not all of them, must be
broken. For boiling to occur, all of the bonds must be broken. As a result, ionic bonds produce
moderate to high melting and boiling points. Ionic bonds are moderate in strength and so
result in moderately hard minerals. The electrical conductivity is generally low, and minerals
with ionic bonds tend to dissolve better in water. In addition, because the charge on ions is
evenly distributed around the surface of the atom, or nondirectional, a cation tends to evenly
distribute as many anions as possible over its entire surface area.
Covalent bonds are different from ionic bonds in that electrons are shared between atoms of
similar charge as opposed to electrons being donated by a cation to an anion. Covalent bonds
form when the electron clouds of separate atoms draw near and overlap, enabling electrons
to be shared. In covalent bonds, each participating atom usually contributes electrons,
resulting in a strong bond. Covalent bonds are common between atoms and ions of the same
element, such as the noble gases.
Minerals with covalent bonds tend to be hard and insoluble. Diamond is one example.
Covalent bonds produce high melting and boiling points and low conductivities. The forces
that bind the atoms tend to be localized in the vicinity of the shared electrons and so are
highly directional. This often yields a lower degree of crystal symmetry.
Because of strong intermolecular hydrogen bonding, H2O, HF, and NH3 exist as associated
molecules. Therefore, their melting and boiling points are much higher than those of the
corresponding hydrides in their respective groups.
The compounds having hydrogen bonding show abnormally high melting and boiling points.
The high melting and boiling point of the compound containing hydrogen bonds is due to the
fact that some extra energy is needed to break these bonds.
▪ In aqueous solution, HF dissociates and gives the difluoride ion instead of fluoride ion.
This is due to hydrogen bonding in HF.
▪ The molecules of carboxylic acids exist as dimer because of the hydrogen bonding.
The molecular masses of such compounds are found to be double than those calculated
from their simple formula.
▪ Polar compounds dissolve in water due to hydrogen bonding. The polar molecules are
attracted to water molecules through hydrogen bonding, and thus they dissolve easily in
water.
Geometry or Shapes of molecules

The geometry or shape of a molecule as found by experimental methods can be explained on
the basis of either of the following:
1. Hybridisation
2. Valence Shell Electron Pair Repulsion Theory (VSEPR Theory).
Valence Shell Electron Pair Repulsion Theory (VSEPR Theory)

This theory was given by Sidgwick and Powell in 1940. The theory is primarily based upon the
fact that in a polyatomic molecule, the direction of bonds around the central atom depends
upon the total number of electron pairs (bonding as well as non-bonding) in its valence shell.
These electron pairs place themselves as far apart as possible in space so as to have minimum
repulsive interactions between them. The minimum repulsions correspond to the state of
minimum energy and maximum stability of the molecule. The main points of the theory are:
1. The shape of the molecule containing only two atoms is always linear e.g., O2, H2, N2 etc.
2. For the molecules containing 3 or more atoms, one of the atoms is called the central atom
to which other atoms are linked.
3. If the central atom is linked to similar atoms surrounded by bond pairs of electrons only,
the repulsion between them is similar. As a result, the shape of the molecule is
symmetrical and the molecule said to have a regular geometry.
For example, CH4, BF3, and CO2 have regular geometry: tetrahedral, trigonal (triangular
planar), and linear, respectively.
4. The electron pairs surrounding the central atom repel each other. Consequently, they stay
as far apart as possible in space to attain maximum stability.
5. If the central atom is linked to different atoms or surrounded by bond pairs as well as lone
pairs of electrons, the repulsions between them are different. As a result, the molecule has
an irregular or distorted geometry.
Lone pair − Lone pair (lp−lp) > Lone pair − Bond pair (lp−bp) > Bond pair −Bond pair (bp−bp).
Let us now apply VSEPR theory to predict the shapes of a few simple molecules:
1. Shape of ammonia molecule

The central atom in NH3 is nitrogen which has five valence electrons. Three of these electrons
are mutually shared with three hydrogen atoms to form three N⎯H bonds.
Also, according to hybridization concept, the nitrogen atom undergoes sp3 hybridisation and
forms four sp3 hybrid orbitals, out of which three contain one electron each and form bonds
with three hydrogen atoms, while fourth sp3 hybrid orbital contains a lone pair of electron and
hence cannot participate in the bond formation.
2px 2py 2pz Sp3 hybrid orbitals

2px 2py 2pz
2p
2s
1s
Nitrogen atom in Nitrogen atom in Nitrogen atom in

ground state excited state hybridised state

The arrangement of these electron pairs is tetrahedral. The expected H⎯N⎯H bond angle is
109.50. However, the bond angle in NH3 is found to be 1070. According to VSEPR theory, the
presence of lone pair causes some distortion in the geometry. The lone pair repels the bond
pairs. As a result, the three N⎯H bonds move slightly closer, thereby decreasing the H⎯N⎯H
bond angle from normal 109.50 to 1070. As a result, ammonia acquires trigonal pyramid or
pyramidal shape.
Trigonal pyramid or pyramidal shape of ammonia
The molecules like H3O+, PCl3 & NF3 also have same shape like ammonia.
2. Shape of water molecule

The central atom of in H2O is oxygen which has six valence electrons. Two of these electrons
are mutually shared with two hydrogen atoms to form three O⎯H bonds.
Also, according to hybridization concept, the oxygen atom undergoes sp3 hybridisation and
forms four
sp3 hybrid orbitals out of which two contain one electron each and form bond with two
hydrogen atoms, while third and fourth sp3 hybrid orbital contains a lone pair of electron and
hence can not participate in the bond formation.
It is shown as follows:
2px 2py 2pz Sp3 hybrid orbitals
2px 2py 2pz
2p
2s
1s
Oxygen atom in Oxygen atom in Oxygen atom in

The arrangement of these electron pairs is tetrahedral. The expected H⎯O⎯H bond angle is
109028. But experimentally, the bond angle in H2O is found to be 104.50. According to VSEPR
theory, the presence of two lone pair causes distortion in the geometry. The reason for the
still lesser bond angle in H2O than in NH3 is that in this case there are two lone pairs of
electrons are present which repel the bond pairs. Thus, in this case the repulsions are more
than those in the case of NH3 molecule.
As a result, the two O⎯H bonds move more closer, thereby decreasing the O⎯H bond angle
from normal 109.50 to 104.50. Thus, water is V-shaped or bent molecule.
V-shaped or bent molecule of water
3. Shape of PCl5molecule
The central atom in PCl5 has five valence electrons. These electrons are mutually shared with
five chlorine atoms to form five P-Cl bonds.
Also, according to hybridization concept, the Phosphorous atom undergoes Sp3d hybridization
and form fie sp3d hybrid orbitals which acquires trigonal bipyramidal shape.
P(15): 1s2, 2s2, 2p6 ,3s2, 3px1 , 3py1, 3pz1,3d0.
In Sp3d hybridization the intermixing of one ‘s’, three ‘p’ and one ‘d’ orbitals are taking place
which generates five new type of hybrid orbitals. In excited state firstly one electron jump to
one of the 3p orbitals and make two paired electrons in 3px orbital. Finally, one electron from
3px will jump to two orbitals of 3d subshell and thus acquires all single electrons in 3p subshell.
This is energetically more stable.

Sp3d1 hybrid
orbitals
3d
3p
3s
Phosphorous atom Phosphorous atom Phosphorous atom in

in ground state in excited state hybridised state
4. Shape of SF6 molecule

The central atom of SF6 is sulphur which has six valence electrons. These electrons are
mutually shared with six fluorine atoms to form six S⎯F bonds.
Also, according to hybridization concept, the sulphur atom undergoes sp3d2 hybridisation and
forms six sp3d2 hybrid orbitals which acquires octahedral geometry.
S(16): 1s2, 2s2, 2p6 ,3s2, 3px2 , 3py1, 3pz1,3d0.
In sp3d2 hybridisation the intermixing of one ‘s’,three ‘p’ and two ‘d’ orbitals are taking place
which generates six new type of hybrid orbitals. In excited state firstly one electron jump to
one of the 3p orbitals and make two paired electrons in 3p y orbital as well, together with 3px
orbital. Finally, one electron each from 3px and 3py will jump to two orbitals of 3d subshell and
thus acquires all single electrons in 3p subshell. This is energetically more stable.

 It is important to note that third shell has 3d subshell. But initially there is no electron in it
(shown with 3d0). After the hybridization two orbitals of 3d subshell acquires one electron
each.
Sp3d2 hybrid
orbitals
3d
3p
3s
Sulphur atom in Sulphur atom in Sulphur atom in

Octahedral geometry of SF6
*******
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NCUK -Chemistry Department Page:1

➔ Ionic and covalent bonding.

➔ Duet Rule and Octet Rule in terms of stabilising atoms.

➔ The nature of covalent bonding. Basic properties of non-polar and polar

➔ The electron sea model of metallic bonding. Properties of metallic bonds.

➔ The nature of van der Waals intermolecular forces. Examples of compounds.

➔ The nature of dipole-dipole intermolecular forces. Examples of compounds.

➔ Comparison of intermolecular bond strengths and properties within

➔ Describe the solid state structures of giant covalent macromolecules including

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C6 – Understand the formation of dative bonds in terms of donation of lone pairs of

C8 – Explain the concept of electronegativity.

C12 – Understand the difference between intermolecular and intramolecular bonding.

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1. By sharing of electrons. This can occur in two ways, as follows:

The Lewis Structure

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10 electrons around P 12 electrons around S 14 electrons around I (iodine)

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4. van der Waal’s forces

1. Covalent Bonds A covalent bonding is a type of force of attraction which binds

Characteristics of Covalent bonds

Examples of Covalent bonds

1. Covalent bond in hydrogen molecule.

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3. Covalent bond in oxygen (O2)

4. Covalent bond in nitrogen (N2)

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5. Covalent bond in HCl

7. Covalent bond in CH4

8. Covalent bond in C2H4

Modern Concept of Covalent Bond According to modern theory of chemical bonding,

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New forces of attraction

New forces of repulsion

New forces of attraction

 No interactions at large distances.  Interactions starts as the atoms come closer

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Inter nuclear distance

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Same way, the formation of H⎯F molecule is explained as below:

Formation of H-F molecule

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Bond energy or Bond dissociation energy

Factors affecting bond energy 

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Bond length is expressed in terms of Angstrom ( 1A0 = 10¯10 m). It is determined

Factors affecting bond length 

C≡C < C= C < C− C

sp3, C−H > sp2, C−H > sp, C−H

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Polar & Non-Polar Covalent Bonds

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Non polar covalent bond between H-atoms

Polar covalent bonds in HCl

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