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CHEMICAL BONDING (General Concepts)

Introduction
 Chemical bonding is the union of two or more
atoms involving the redistribution of electrons
either by transfer or sharing between themselves,
so that all of them acquire the stable noble gas
configuration of minimum energy
 Intra-molecular bonds bind atoms within a
molecule or compound with each other
(eg. one Cl atom with another Cl atom as in the
covalent bond of the Cl2 molecule)
 Inter molecular forces (bonds) bind compounds
or molecules together
(eg. one H2O molecule to another as in the hydrogen
bond)
There are two principle classes of bonding:
(1) Bonding which involves the transfer of electrons
between atoms known as ionic bonding or
electrovalent bonding (ions are produced)
(2) Bonding which involves the sharing of
electrons known as covalent bonding (occurs in
molecules)

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The Octet Rule

Atoms tend to gain, lose or share electrons until
they have achieved an outer shell that contains an
octet of electrons (eight electrons)
(The rule is only suitable for the representative
elements; and the hydrogen atom tend to gain, lose or
share only 2 electrons)
Lewis symbols (Lewis structures)
The Lewis symbol for an element consists of the
chemical symbol the element surrounded by a
number of dots (or some other marks), which
represent the atom's valence electrons
eg Element Electron configuration Lewis symbol
H 1s1 .H
C 1s2 2s2 2p2 :C:
Al 1s2 2s2 2p6 3s2 3p1 . Al :
The Lewis symbols for representative elements may
be predicted from their groups in the periodic table:

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Ionic bonds (Electrovalent bonds)

Ionic bonds are formed when electrons are
transferred from one atom to another
 The atom which donates electrons becomes
positively charged (cations) and the atom which
receives electrons becomes negatively charged
(anions)
 The electrostatic attraction between the
oppositely charged ions is called the ionic bond
The formation of the ionic bonds in LiF and CaCl2
may be shown by the following Lewis structures:

Li + F Li+ F -
 One Li atom loses one electron to form Li+
One F atom gains one electron to form F-
Li+ and F- ions attract to form LiF

Cl 2+ -
Ca Ca 2 Cl atau CaCl2
Cl
 One Ca atom loses 2 electrons to form Ca2+
Two Cl atoms gain one electron each to form 2Cl-
Ca2+ and Cl- ions attract to form CaCl2
(Poliatomic ions, such as HCO3- and SO42-, may form
ionic bonds with metals such as MgSO4 and KHCO3)

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Conditions for the formation of ionic bonds

 The two atoms must be different (generally, a metal
from group 1A-3A and the second non-metal from
group 5A-7A)
 The atom which loses electrons must have a low
ionization energy (so that electrons are easily
removed)
 The atom which gains electrons must have a high
electron affinity (so that electrons are easily
accepted)
 The lattice energy released must be high so that
the ionic structures that form are stable (Lattice
energy is energy released by a process in which
isolated ions come together to form a crystal or ionic
compound)
Sample problem 1
X is an element in group 2A and Y is in Group 5A
(a) Determine the type of bonding which occurs
when X reacts with Y
(b) Use Lewis Structures to show the formation of
the compound produced

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Solution:

Covalent Bonds
 A covalent bond is formed due to sharing of
electrons between two atoms
 When atoms (either similar or dissimilar) taking part
in a chemical combination are short of electrons
to complete the nearest inert gas configuration,
the combination between them takes place by
sharing electrons
 The bond established between atoms by this
process of sharing is known as a covalent bond
 A covalent linkage may be expressed by a dash
‘’ in writing the formula
(Generally, non-metals and non-metals form covalent
bonds but small metallic atoms such as Be, B and Li
form covalent bonds with non-metals because they do

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not readily donate their electrons : eg BeCl2, BCl2 and

LiCl are covalent in nature)
The following figures show Lewis structures of the
formation of covalent bonds in the Cl2, O2 and N2
molecules
 The sharing of one pair of electrons between two

atoms as shown below is referred to as a single

bond (The single bond is known as a sigma bond)

 The sharing of two electron pairs between two

atoms as shown below is referred to as double
bond (The 1st single bond is known as the sigma
bond and the 2nd bond is known as the pi bond: the
pi bond is weaker than the sigma bond)

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 The sharing of three electron pairs between two

atoms is referred to as triple bond (There is one
sigma bond and two pi bonds in a triple bond)

Steps to writing Lewis Structures (covalent bonds)

Example 1
Write the Lewis Structure of NF3
 Step 1: Count the total valence electrons

1 N atom (Group 5A) has 5 valence e = 1x5e = 5e

1 F atom (Group 7A) has 7 valence e = 3x7e = 21e
 the NF3 molecule has 26 valence electrons
Step 2: Write the skeletal structure
Choose the most symmetrical
arrangement or the central atom must F
be the least electronegative (Hydrogen F N F
atoms are generally bonded to oxygen
atoms)
 Step 3: Use two valence electrons to

form each bond in the skeletal .F.

F :N:F
structure

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 Step 4: Complete the octets (but only 2 for H) of the

outer atoms by distributing the remaining valence
electrons in pairs
 Place remaining electrons on the central atom
.. ..
: .F. : . . : .F. : . .
.. ..
: F: N :F :  : F: N :F :
.. .. .. .. .. ..

Example 2
Write the Lewis Structure of CO 2
3

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Bonding electrons are pairs of electrons that take

part in bonding and non-bonding electrons are
unshared electrons
The bond order is the number of pairs of bonding
electrons
As the bond order increases the bond length
between the same elements decreases
Formal charge and the selection of Lewis Structures
 The formal charge is the apparent charge on an
atom in a molecule or poly-atomic ion
 When several Lewis structures are possible,
those with the smallest formal charges are the
most stable and preferred
 The formal charge on any atom in a Lewis
structure is calculated as follows:
Number of valence e in the
Formal charge =
valence shell of the atom
Number of bonds Number of unshared
to the atom electrons

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Sample problem 2
Determine the formal charges of the atoms in CO 32 
Solution

Sample problem 3
Write Lewis structures for CO2 and determine the
most preferred structure

Solution

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Resonance Structures
There are some molecules or ions for which we
cannot write Lewis structures that agree with
experimental bond lengths or energy data
The actual structure of these molecules is the
resonance hybrid, which is a hybrid (‘average’) of a
number of resonance structures
The symbol '  ' is used to imply that the true
hybrid is a composite of the contributing resonance
structures
O O O
O C O O C O O C O

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Coordinate bonds
 A coordinate bond is a covalent bond in which
both shared electrons originate from one of the
joined atoms
 The coordinate bond may be shown by using the
symbol '' to designate the source of shared
electrons
Examples: The pair of electrons that bind the N
atom to another atom in the NH4+ ion and the
NH3BCl3 molecule originate from N only
H H +
H N : + H+ H N H
H H
H Cl H Cl
H N + B Cl H N B Cl
H Cl H Cl
Sample problem 4
The H2O molecule forms a coordinate bond with H+
to form the H3O+ ion. Show this bond on the Lewis
structure of H3O+
Solution

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Polar covalent bonds

 Polar bonds are formed when one of the elements
attracts the shared electrons more strongly than
the second element (These bonds are somewhere
between covalent and pure ionic bonds in character)
 There is asymmetry in the distribution of electron
density (the electrons being shifted towards the more
electronegative atom)
eg the polar covalent bond of H-Cl:

 The unequal sharing of electrons leads to

fractional (partial) electrical charges on atoms
represented by the Greek letter 
Polar covalent bond Pure covalent bond
  Cl Cl
H : Cl :

Comparison of the electron density of a pure covalent

and polar covalent bond

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 The dipole moment,  (in units of Debye) is the

measure of polarity of a bond
 Polar and non-polar molecules are differentiated
by their shape and the resultant dipole moments
Polar molecules
 contain atoms of different elements
 are ‘asymmetric’
 have dipole moments (  0)
eg HCN H - C  N
+   -
HCN is a polar molecule because of its asymmetric
shape: the resultant polarity is enhanced towards N
because it is most electronegative
eg CO2 O=C=O
- + -
CO2 is a non-polar molecule because the molecule
is symmetrical: the resultant polarity is cancelled out
(= 0)
eg H2O
O
H H
H2O is a polar molecule because of its asymmetric
(bent) shape: the resultant polarity is enhanced
towards the oxygen atom (more electronegative)

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Limitations of the octet rule

Some atoms are stable with
Cl B Cl
incomplete octets (possess less than (stabil deng
Cl
eight electrons)
There are atoms which are stable F F F
with expanded octets (possess more P (stabil
F F
than eight electrons) F

Properties of covalent and ionic compounds

Ionic Covalent
 Not molecular form  Molecular form
 Particles are charged  No charged particles
 Strong binding forces  Weak binding forces
 High melting and  Low melting and
boiling points boiling points
 Soluble in water and  Soluble in non-polar
polar solvents and organic solvents
 Ions conduct electricity  Polar molecules may
in solution and molten conduct electricity
state
* Some polyatomic ions bonded to metals have both
covalent and ionic bonds eg NaHCO3 etc

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Intermolecular forces
van der Waals forces
 The van der Waals forces are weak forces of
attraction between neutral molecules or particles
 There are 2 types of van der Waals forces:
 Dipole-dipole forces are permanent attractive

forces between polar molecules

When polar molecules align, the positive end of
the molecule will attract the negative end
+ - + - + -

- + - + - +

 Dipole-induced dipole forces (London dispersion

force)
A temporary dipole moment may be induced due
to the fluctuation of electron distribution within a
molecule
When molecules with the temporarily induced
dipoles align, they attract each other temporarily

+ -
-
+

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 Properties related to the van der Waals force

 When molecules differ widely in their molecular

masses, the larger molecule has the stronger

attraction (because more electrons are contained in
the molecule)
 When molecules differ slightly in their molecular

masses, the more polar molecule has the stronger

attraction
 Molecules with strong van der Waals forces have

high boiling and melting points

Sample problem 5

You are given Cl2, CCl4 and ClNO. Arrange the

compounds in increasing order of their boiling
points, Tb and explain your answers

Solution

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Hydrogen bonds
 The hydrogen bond is a permanent attraction
which occur between molecules that contain
hydrogen atom covalently bonded to small highly
electronegative atoms such as N, O and F
 Relative strengths:
Covalent bond  10x hydrogen bond
 100x van der Waals force
 Hydrogen bonds are generally represented by
dotted lines
H H
F F F O O
H H
H H H H H
O

Hydrogen bonds
Ikatan hidrogen H H H
O O
H

Hydrogen bonds in HF, H2O and NH3

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 Hydrogen bonds increase the boiling points of

compounds that contain them because it takes
more energy to break the extra attraction between
thedidih
Takat liquid
(oC)particles to form gases
100 H2O

HF

0 H2Te
NH3 H2Se SbH3
H2S AsH3 HI
HCl HBr SnH4
PH3
-100 GeH4
SiH4

CH4

-200
2 3 4 5 Kala
 The boiling points of the hydrides in group 4A
(CH4, SiH4, GeH4 and SnH4) increase as the mw
increase because as the sizes of molecules
increase the van der Waals forces increase
 The boiling points of the hydrides in group 5A-7A
increase as mw increase but for HF, H2O and NH3
the boiling points are higher than predicted due to
the presence of hydrogen bonds that are
relatively difficult to break

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 The boiling point of H2O is exceptionally high

because there are 4 hydrogen bonds for every
water molecule


Sample problem 6

Explain the increasing order of boiling points of the

following hydrides:
HCl < HF < H2O
Solution

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 Resonance structures
 A resonance hybrid is the actual structure of a
molecule or polyatomic ion taken as a composite
(average) of the resonance (contributing)
structures
 Resonance structures are Lewis structures that

contribute to the hybrid structure

(a) SO2
Resonance structures

Resonance hybrid

(b) HNO3
Resonance structures

Resonance hybrid

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Not all Lewis structures are resonance structures
The following conditions must be applied when
selecting stable resonance structures:
(1) All atoms in resonance structures must have
similar positions:
O = C = N-  O - C  N-
but N = O - C-  C - N = O-
because the position of atoms are different
(2) Bonded atoms must not have the same formal
charge :
+ O  + O_
F N _ F N
O O

+ O_ O
+ +
F N Non resonance
bukan resonans F N _
_
O O
(3) Formal charges on atoms must be smallest and
suited to the electronegativity
O = C = N-  O - C  N-
but O = C = N-  +O  C - N2-
because 2- is large and O is more electronegative
than N

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 Metallic Bond
Bonding in metals may be explained by
 The Electron Sea Model
 The Band Theory
Electron Sea Model
 The metallic bond consists of atoms held together
by their valence electrons that are moving freely
throughout the structure in 3-dimensions
 The electrons are detached from their parent atoms
and are frequently referred to as an electron sea
 The atoms are held together by strong forces of
attraction between the positive nuclei and the
delocalised electrons
 Strength of metallic bond  the positive charge of the
nucleus and the number of valence electrons
Malleability and ductility of metals
Metals are described as malleable (can be beaten into
sheets) and ductile (can be pulled out into wires)
because of the ability of the atoms to roll over each
other into new positions without breaking the
metallic bond (figure a)
[Compare this to the ionic solid (b), which will break
when oppositely charged ions align]

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The difference between the structure of (a) metal bonds
(in solid metal) and ionic bonds (in ionic solids)
Electrical conductivity
 Electrons carry electrical charges by flowing
freely through a metallic structure (crossing grain
boundaries)
Thermal conductivity
 A metal conducts heat by picking up heat energy
as additional kinetic energy (making them move
faster)
 The energy is transferred throughout the rest of
the metal by the free moving electrons
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Melting and boiling points
 Most metals have high melting and boiling points
because metallic bonds are strong
 The strength of the bond depends on the number
of electrons which each atom delocalises into the
sea of electrons and packing (the arrangements of
atoms in the structure)
The Band Theory
The band theory is an expansion of the Molecular
Orbital theory applied to a large number of atoms
 In the basic MO theory, atomic orbitals on two
atoms would combine to form bonding and
antibonding orbitals
Anti-bonding
orbital

Atomic orbitals Bonding

orbital

 Expanding the idea by considering combinations

of 10 atoms, a set of five bonding and five
antibonding orbitals would be obtained

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 5 Anti-bonding
orbitals

5 Bonding
10 Atomic orbitals
orbitals

 If a large number of atoms combine, a large

number of bonding and antibonding orbitals will
be formed so close together in energy that they
create bands of bonding and antibonding orbitals

Conduction
band
Band gap

Valence
band

Insulator Semiconductor Conductor

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 An insulator has a large band gap between bands
An insulator has very low electrical conductivity, but
the conductivity increases with an increase in
temperature (eg Diamond has a band gap of 502 kJ
mol-1)
 A semiconductor has a small band gap
Semiconductors show electrical conductivity that
increases with increasing temperature, opposite to
that of metals (eg Si: band gap = 100 kJ mol-1 and Ge:
band gap = 67 kJ mol-1)
 A conductor has no band gap between the bands
 The conduction band is the band that are high in

energy and are generally half filled or empty

In semiconductors, it is the band that accepts the
electrons from the valence band
 The valence band is the band that are low in

energy and are generally full in semiconductors

(When heated, electrons from this band can jump
across the band gap into the conduction band,
making the material conductive)
(The twinkle or shine in substances is produced by
the energy released when electrons jumps back into
the valence band)