CHEMICAL BOND

Bond: it is the electrostatic force of attraction between bonding atoms. When a bond is formed
the force of attraction and repulsion are at equilibrium.

Types of bond

There are three types of bond – ionic, covalent and metallic.

Type of bonding Ionic Covalent Metallic

Nature of bonding Electrostatic attraction between Shared pair of electrons between Attraction between lattice of
positive and negative ions. atoms. positive metal ions and
delocalised outer shell electrons.

Types of structure which Giant ionic crystals Simple covalent and Giant Giant metallic structure.
have this type of covalent network.
bonding

Strength of bonds The smaller the ions and the
greater the charge on the ions,
the stronger the attraction
between the ions (usually). This
is due to a greater charge density
within the structure.
The shorter the bond, the
stronger the bond (usually).
Double bonds are stronger than
single bonds, while triple bonds
are stronger than double bonds.
The smaller the metal ions, the
greater the charge on the ions,
and the more delocalised outer
shell electrons there are, the
stronger the attraction between
the ions and electrons (usually).
This is due to a greater charge
density within the structure.

There is also special type of covalent bond called as dative or coordinate covalent. It is such type of bond in which
shared pair of electrons are contributed by single bonding atom. This bond is represented by an arrow , where head
points to that atom which does not contribute electrons.

There are also three types of forces between molecules (van der Waals’ forces, dipole-dipole attractions and
Hydrogen bonds). These are NOT bonds because they are too weak.

Formation of ions

Ions can be formed when a metal reacts with a non-metal. The metal atoms lose electrons to form positive
ions while non-metal atoms gain electrons to form negative ions (both obtaining full outer shells).
IONIC BOND

An ionic bond is an attraction between oppositely charged ions, which are formed by the transfer of
electrons from one atom to another.

Eg In sodium chloride, each sodium atom transfers an electron to a chlorine atom. The result is a sodium ion and a
chloride anion. These two ions attract each other to form a stable compound.

oo

Na o o
Cl o
x
oo

+ -
oo

o o
Na Cl
x o

oo

+ -
oo

o o
Na Cl
x o

oo

Remember that ionic bonds are the attraction between positive and negative ions. For the formation of ionic bond one
of the bonding atoms should have low ionisation energy where the other should have high ionisation energy.
Covalent bonds

Covalent bonds can be formed when a non-metal reacts with a non-metal. The atoms share electrons to obtain full
outré shells. Two shared electrons make a single bond, four shared electrons make a double bond, and six shared
electrons makes a triple bond. For formation of covalent bond the bonding atoms should have high ionisation
energy and have half filled atomic orbitals.

For example in water:

H H H
x x H
o
O o O
x x xx

Atoms Group 4 atoms Group 5 atoms Group 6 atoms Group 7 atoms H

Number of covalent bonds 4 3 2 1 1

How to draw “dot-cross” diagrams

1) Draw a stick diagram (use the help above to work out how to draw the stick diagram).
2) Re-draw the molecule without the sticks.
3) Draw a dot and a cross instead of each stick (i.e. lx for a single bond, lxlx for a double bond, etc.). Dots and
crosses represent electrons from different atoms.
4) Work out how many electrons there are in the outer shell of each atom (e.g. atoms in Group 7 have 7 electrons in
their outer shell), and then add in any of these electrons that are not already drawn on in the covalent bonds.

Note that elements in period 3 and beyond can fit more than 8 electrons in their outer shell (due to availability of d
orbitals in the shell). For example, P and S atoms can have more than electrons in the third shell (as extra electrons
can occupy the 3d orbitals).

For ions, any electric charge means that the ion has more or less electrons than the neutral atoms would have. For
example, a 1+ ion has one less electron than the atoms, and a 2- ion has two extra electrons.

In your book, draw stick and then dot-cross diagrams for each of the following molecules and ions.

1) F2 4) H2 S 7) PF3 10) CO2 13) SO42- 16) C2H2 19) BeCl42-

2) NH3 5) CH4 8) PF5 11) NH4+ 14) BCl3 17) NO3- 20) IF4+
3) O2 6) H2 9) SO2 12) AlCl4- 15) SF6 18) BeCl2
Coordinate Covalent bonds: It is the special type of covalent bond in which shared pair of electrons are
contributed by single bonding atom. This bond is represented by an arrow, where head points to that atom which
does not contribute electrons. E.g. CO, SO2, SO3, NH4+,H2SO4,H2SO3,HNO3,Al2Cl6 etc.

NH4+

NH3⟶BF3
CO

Al2Cl6

HNO3
Electronegativity: It is the tendency of an atom to pull the bonded pair of electrons towards
itself in a covalent bond.

Electronegativity =

H He
2.1
Li Be B C N O F Ne
1.0 1.5 2.0 2.5 3.0 3.5 4.0
Na Mg Al Si P S Cl Ar
0.9 1.2 1.5 1.8 2.1 2.5 3.0
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
0.8 1.0 1.3 1.5 1.6 1.6 1.5 1.8 1.8 1.8 1.9 1.6 1.6 1.8 2.0 2.4 2.8
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
0.8 1.0 1.2 1.4 1.6 1.8 1.9 2.2 2.2 2.2 1.9 1.7 1.7 1.8 1.9 2.1 2.5
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
0.7 0.9 1.1 1.3 1.5 1.7 1.9 2.2 2.2 2.2 2.4 1.9 1.8 1.8 1.9 2.0 2.2
7

Factors that affect electronegativity:

1. Nuclear charge
The higher the nuclear charge, more will be the electronegativity value of an element, since the nucleus
will be able to attract or pull more electrons towards itself.

2. Atomic size
Size of the atom is inversely proportional to electronegativity value. The smaller the element, higher is its
nucleus's reach towards the outer shell. Thus, more will be the electronegativity. An example of this is
Fluorine, the first member of the halogen series. 

Fluorine is the most highest electronegative element available and is the smallest one too.

3. Screening effect or shielding effect

If the outermost electrons shields the nucleus effectively, the electronegativity of the element decreases.

Electronegativity trend down a group: It decreases down the group.

Electronegativity trend across a period: It increases across the period.

Polarisation of bonds no electronegativity large electronegativity
difference difference

- +
- + - +
x Y X Y x Y x Y

polarisation of covalent bonds polarisation of ionic bonds

pure covalent polarised covalent polarised ionic pure ionic

(favoured by + ions with
high charge denisty - i.e.
small / high charge)

100
90
80
70
% ionic characater

60
50
40
30
20
10
0
0 0.5 1 1.5 2 2.5 3 3.5 4
difference in electronegativity

Trend in bonding of Period 3 chlorides

NaCl Ionic

MgCl2 Ionic

AlCl3 Covalent

SiCl4 Covalent
Polar bonds and polar molecules

When the two atoms in a covalent bond have different electronegativities, the electrons are attracted more towards
the more electronegative atom. This creates a slight charge separation with the more electronegative atoms being d-
and the less electronegative atom being d+. This charge separation creates a dipole and makes the bond polar.

Many molecules with polar bonds are themselves polar and have a permanent dipole.

H 
  O
e.g. H F C Cl
H H H
H  

However, some molecules with polar bonds do not have a permanent dipole as the bond polarities cancel each other
out.


Cl


e.g. O C O  C Cl
Cl
Cl


Which of the following molecules are polar?

Cl F H
C H P C F
Br Br Cl F H Cl F
B
F F
Cl F F H
FORCES BETWEEN MOLECULES
There are three types of forces between molecules (intermolecular forces).If there were no force of attraction
between the molecules every covalently substance should be in gaseous state, this is not true as some covalent
substances are in solid and liquid state. Thus there must be some sort of attraction between the molecules.Different
types of intermolecular interactions are:

1. Van der Waals' forces

 Even in molecules with no polar bonds, there are temporary dipoles due to uneven electron distribution due to
the constant movement of electrons.

 This induces a temporary dipole in a neighbouring molecule, producing a temporary induced dipole-dipole
attraction.

 The bigger the molecule (i.e. the more electrons), the greater the van der Waals' forces (e.g. C 2H6 boiling point
-89°C, C3H8 boiling point -42°C).

2. Permanent dipole-dipole attraction

 Some molecules with polar bonds have an overall dipole (e.g. + H–Cl ) [although not all do (e.g. CCl4 - the
individual dipoles cancel each other out)].

 There are attractions between these permanent dipoles in neighbouring molecules (e.g. between H-Cl
molecules).

3. Hydrogen bonding

 This is a special case of permanent dipole-dipole attractions – where an H atom is bonded to a very
electronegative atom (i.e. F, O, N)

 The polar bond leaves the H nucleus exposed as H only has one electron.

 Therefore there is a strong attraction from the lone pair on the N, O or F of one molecule to the exposed H
nucleus of another molecule.

 This is simply a strong intermolecular force – it is NOT a bond!



H 
H
 
 N
e.g. NH3 N H
H
H
H 


e.g. H2O

e.g. HF
The strength of intermolecular forces

 H-bonding > permanent dipole-dipole > van der Waals'

 Covalent bonds are very strong (values in hundreds of kJ mol -1). The forces between molecules are much
weaker, with van der Waals’ forces being in units of kJ mol -1 and hydrogen bonds in tens of kJ mol-1 (dipole-dipole
attractions are in between).

Some comparisons

Molecule CH4 HCl H2O

Boiling points (ºC) -162 -85 100

Intermolecular forces Vander waal’s Permanent dipole Hydrogen bond

Boiling points of hydrides of Groups 4, 5, 6 and 7

Matter can have different structure. Five different type of structure of matters are:

Monatomic Simple molecular Giant covalent Ionic Metallic

Substances Group 0 elements Elements: Elements: Si, diamond, Compounds: Elements: metals
H2 O2 N2 F2 Cl2 Br2 I2 graphite metal with non-metal
S8 P4
Compounds: SiO2
Compounds:
non-metal with non-metal

What the Individual atoms with Individual molecules with Lattice structure in which Lattice structure of Lattice structure of metal
structure is very weak forces weak forces between all atoms are joined to positive and negatively ions with outer shell
between them them (atoms within others by covalent bonds charged ions (ions are electrons free to move
molecules are joined by held together by through the structure
covalent bonds) attraction between the +
and – ions (this +/-
attraction is known as an
ionic bond, though it is
just an electrostatic
attractive force))

The formula Just the symbol e.g. H2O e.g. SiO2 e.g. MgCl2 Just the symbol
e.g. Ar each molecule contains ratio of Si:O atoms is 1:2 ratio of Mg2+:Cl- ions is e.g. Fe
1 O and 2H atoms through the structure 1:2 through the structure

Melting and Very low low Very high Very high Very high
boiling points

Conductivity Bad conductor insulator Good insulator Insulator in solid state Good conductor
but conductor in molten
or aqueous form.

Solubility in Insoluble in polar Soluble in polar solvents Insoluble in both polar Soluble in polar solvents Insoluble in both solvents
water solvents and non polar solvents but insoluble in non polar
solvents

Solid – + – + – + –
+ – + – + – +
– + – + – + –
+ – + – + – +
– + – + – + –

Liquid – + + – – +
– + +
+ – + +
+ + –
– + +
– + – + +
+
+ + + – +
– +
– +
+ – + – – + +

Gas
_

+ +

–
+
_
– _
+
+
SHAPES OF SIMPLE COVALENT MOLECULES:
Electrovalent bonds are the electrostatic attractions that exists between oppositely charged ions .Since ions radiate a
spherically symmetrical positive or negative field, ionic bonds are non-directional. However covalent bonds are
formed by the overlap of atomic orbitals and there is particular orientations in which there is maximum overlap. Thus
they are directional and take particular shape. The shape of simple covalent molecules or ions is given by Valence
Shell Electron Pair Repulsion Theory.(VSEPR theory)

Molecules and ions possess two types of electron pairs:

 Bonding pairs (the two shared electrons in a covalent bond)

 Lone pairs (two electrons in a pair not involved in bonding – also known as non-bonding pairs).

These electron pairs will repel each other as far as possible. The shape of any molecule or ion is a consequence of
these electron pairs repelling each other as far as possible.

Lone pairs are more compact than bonding pairs and provide more repulsion. Consequently, the greatest repulsion
is between two lone pairs, followed by the repulsion between one lone pair and one bonding pair, with the weakest
repulsion between two bonding pairs. Thus order of magnitude of repulsion is lone pair-lone pair ˃ lone pair-bond pair
˃ bond pair-bond pair.

In a molecule or ion with only bonding pairs, the repulsions will therefore be equal. All diatomic molecules and ions
are linear in shape. But for tri atomic and polyatomic molecules and ions ,the shape is predicted using VSEPR theory.

Guidance to help to work out the shape of a molecule or ion:

1) Draw a stick diagram.

2) Add in any lone pairs onto the stick diagram.
3) Count the total number of bonds (double and triple bonds count as singles for this) + lone pairs to work out
the shape.
In general, there are four pairs of electrons in valence shell of central atom so that it satisfies octet state.
However there are cases of violation of octet, either expansion of octet or the molecules may have far less no of
electrons than required for it to be in octet.

When there is presence of a lone pair the bond angle nearly decreases by 2.5°. Eg CH4 has bond angle 109.5°
where as NH3 has bond angle 107 to 107.5° and H2O has bond angle 104.5°.
The chart on this page shows the common shapes.
total number of number of number of
shape Example
electron pairs bonding pairs lone pairs

2 2 0 linear HCN,CO2,C2H2,BeCl2 etc

180º

BF3,AlCl3,CO32-,NO3-,SO3,
trigonal planar C2H4etc
3 0

120º
3
-
GeCl2,CCl2, SnCl2,SO2,NO2
bent
2 1
118º

CH4,SiH4,CCl4,SnCl4,
tetrahedral SO42-,ClO4-,NH4+,PO43-,etc
4 0
109.5º

trigonal pyramid NH3,PH3,NF3,NCl3,ClO3-,H

+
3O ,etc
4 3 1
107º

bent H2O,H2S,SCl2,OF2,
NH2-,ClO2-,etc
2 2 104.5º

PCl5,PF5,SbCl5,etc
trigonal
5 0 120º bipyramid
90º

SF4,SCl4,TeCl4, etc
Distorted
5 89º tetrahedral
4 1 119º OR
119º
89º

ICl3,IF3,ClF3,etc
trigonal planar
2
3 OR
89º
or
120º T-shape
 SF6,SeF6,PF6-,SnCl62-,etc
90º octahedral
6 0

ICl5,BrF5,IF5,etc
89º distorted square
5 1 pyramid
6

-
XeF4,ICl4 etc
90º square planar
4 2

Bonding in metals
Metallic bonding is the attraction between cations and a sea of delocalised electrons. The cations are arranged to
form a lattice, with the electrons free to move between them.

The structure of the lattice varies from metal to metal, and they do not need to be known in detail. It is possible to
draw a simplified form of the lattice:

Example - magnesium

2+
e e 2+
2+
Mg Mg Mg
ee ee e This is a
Mg
2+ 2+
Mg Mg
2+
simplified 2D
form of the
e e ee metal lattice
2+ 2+ 2+
Mg Mg Mg
e e

Properties of metals

a) Electrical conductivity: since the electrons in a metal are delocalised, they are free to move throughout the
crystal in a certain direction when a potential difference is applied and metals can thus conduct electricity in the solid
state. The delocalised electron system is still present in the liquid state, so metals can also conduct electricity well in
the liquid state.

b) Melting and boiling point: although not generally as strong as in ionic compounds, the bonding in metals is
relatively strong, and as a result the melting and boiling points of metals are relatively high.

Metal Na K Be Mg
Melting point/ oC 98 64 1278 649
Boiling point/ oC 883 760 2970 1107

Smaller ions, and those with a high charge, attract the electrons more strongly and so have higher melting points than
larger ions with a low charge. Na has smaller cations than K so has a higher melting and boiling point. Mg cations
have a higher charge than Na so has a higher melting and boiling point.
c) Other physical properties: Since the bonding in metals is non-directional, it does not really matter how the
cations are oriented relative to each other. The metal cations can be moved around and there will still be delocalized
electrons available to hold the cations together. The metal cations can thus slip over each other fairly easily. As a
result, metals tend to be soft, malleable and ductile.