2.

Chemical Bonding
and
Molecular Structure
CHEMICAL BONDS

Is the force of attraction

between any two elements
in a compound.
 Chemical Bond
• A force of attraction that holds two atoms together.
• Involves the valence electrons

Sodium Carbon Oxygen

1 Valence Electron 4 Valence Electrons 6 Valence Electrons
TYPES OF BOND

 Ionic (electrovalent)
- strong bonds
 Covalent

- dative covalent (co-ordinate)

 Metallic

- sea of electrons
IONIC BONDS

 The ionic bond is the force of attraction

that binds together unlike charged ions
to form a chemical compound.
Ionic Bonding
 An ionic bond is an electrostatic attraction between
oppositely charged ions
 Ionic bonding occurs between a metal and a non-metal and
involves the transfer of electrons from the metal to the non-
metal
 The bigger the difference in electronegativity between the two
atoms, the more ionic the bond
 Ionic bonds are strong, consequently the melting and boiling
points of ionic compounds are very high
Ionic Bond Formation
 Bond formed due to the gain or loss
of electrons in atoms i.e. due to
transfer of electrons between atoms.

 When an atom loses an electron it is a

POSITIVE charge.
 When an atom gains an electron it is a
NEGATIVE charge
 These newly charged atoms are now
called IONS
 Example: NaCl (Common Salt)
 IONIC BONDS
 example

METALS
•have a low/high number of valence electrons.
•metals lose/gain electrons when bonding.
•form positive/negative ions.

NONMETALS
•have a low/high number of valence electrons.
•lose/gain electrons when bonding.
•form positive/negative ions.
•ions end in –ide
Ionic Bond
Ionic Bond

Cl -1 Na +1

- -
-
- -

- -

++ +
- + + + - -
+ +
- -
- -
-
-
-
Forming ionic compounds
 Ioniccompounds are represented by dot-and-
cross diagrams:
2 electrons transferred
2+

Ca 2.8.8

Ca + O
2-

2.6 O 2.8

CaO, calcium oxide

2.8.8.2
 THE IONIC BOND

FORMATION OF MAGNESIUM CHLORIDE

e¯

Cl

ELECTRON
Mg
TRANSFER

Cl

e¯

Mg ——> Mg2+ + 2e¯ and 2Cl + 2e¯ ——> 2 Cl¯

 THE IONIC BOND
Ionic bonds tend to be formed between elements whose atoms need to “lose”
electrons to gain the nearest noble gas electronic configuration (n.g.e.c.) and
those which need to gain electrons. The electrons are transferred from one
atom to the other.
Sodium Chloride

Na ——> Na+ + e¯ and Cl + e¯ ——> Cl¯

1s2 2s2 2p6 3s1 1s2 2s2 2p6 1s2 2s2 2p6 3s2 3p5 1s2 2s2 2p6 3s2 3p6
or 2,8,1 2,8 2,8,7 2,8,8

An electron is transferred from the 3s orbital of sodium to the 3p orbital of

chlorine; both species end up with the electronic configuration of the nearest
noble gas the resulting ions are held together in a crystal lattice by
electrostatic attraction.
 Physical properties of ionic compounds
Melting point
very high A large amount of energy must be put in to overcome the
strong electrostatic attractions and separate the ions.

Strength
Very brittle Any dislocation leads to the layers moving and similar
ions being adjacent. The repulsion splits the crystal.

Electrical don’t conduct when solid - ions held strongly in the lattice
conduct when molten or in aqueous solution - the ions
become mobile and conduction takes place.

Solubility Insoluble in non-polar solvents but soluble in water

Water is a polar solvent and stabilises the separated ions.

Much energy is needed to overcome the electrostatic attraction and separate

the ions stability attained by being surrounded by polar water molecules
compensates for this
 Properties of Ionic Compounds

CHARACTERISTICS OF IONIC COMPOUNDS

•Hard, brittle solids at room temp
•High melting and boiling points
•Ions are held in a crystal lattice
•Conduct electricity when dissolved in H2O
Born-Haber Cycle
 Lattice Energy
 Lattice energy (the energy binding a crystal lattice together)
is used to measure the strength of bonding in ionic
compounds
 It is defined as follows:
 the enthalpy change when 1 mole of an ionic crystal
lattice is formed from its constituent ions in gaseous form
 An example is:

Na+(g) + Cl-(g)  NaCl(s) HLE = -787 kJ mol-1

 Born-Haber Cycle - NaCl
1 Enthalpy of formation of NaCl
Na(s) + ½Cl2(g) ——> NaCl(s) Na+(g) + Cl(g)

2
Enthalpy of sublimation of sodium
5
Na(s) ——> Na(g) 4
3 Enthalpy of atomisation of chlorine
Na+(g) + Cl–(g)
½Cl2(g) ——> Cl(g)
Na(g) + Cl(g)
4
Ist Ionisation Energy of sodium
3
Na(g) ——> Na+(g) + e¯
Na(g) + ½Cl2(g)
5
Electron Affinity of chlorine
Cl(g) + e¯ ——> Cl¯(g) 2 6

6 Na(s) + ½Cl2(g)
Lattice Enthalpy of NaCl
Na+(g) + Cl¯(g) ——> NaCl(s) 1

Lattice
LatticeEnthalpy
Enthalpyisis exothermic.
exothermic. NaCl(s)
Oppositely
Oppositelycharged
chargedions
ionsare
are
attracted to each other.
attracted to each other.
Step Reaction Process Value

(kJ/mol)

1 Na (s) → Na (g) Sublimation 107.3

2 ½ Cl2 (g) → Cl (g) BDE ½ (243)

3 Na (g) → Na+1 + e- Ionization Energy 495.8

4 Cl (g) + e- → Cl-1 (g) Electron Affinity -348.6

5 Na+1 (g) + Cl-1 (g) → NaCl (s) Lattice Energy -787

6 Na (s) + ½ Cl2 (g) → NaCl (s) Enthalpy of -411

Reaction
 Born-Haber Cycle - MgCl2

1 Enthalpy of formation of MgCl2

Mg(s) + Cl2(g) ——> MgCl2(s) Mg2+(g) + 2Cl(g)

2
Enthalpy of sublimation of magnesium
Mg(s) ——> Mg(g) 5
6
3 Mg (g) + 2Cl(g)
+
Enthalpy of atomisation of chlorine
½Cl2(g) ——> Cl(g) x2
4
4
Ist Ionisation Energy of magnesium Mg2+(g) + 2Cl–(g)
Mg(g) + 2Cl(g)
Mg(g) ——> Mg+(g) + e¯

5 3
2nd Ionisation Energy of magnesium
Mg(g) + Cl2(g)
Mg+(g) ——> Mg2+(g) + e¯
6
2 7
Electron Affinity of chlorine Mg(s) + Cl2(g)
Cl(g) + e¯ ——> Cl¯(g) x2
1
7
Lattice Enthalpy of MgCl2
Mg2+(g) + 2Cl¯(g) ——> MgCl2(s) MgCl2(s)
Solution:

Step Reaction Process E (kJ/mol)

1 Mg (s) → Mg (g) Sublimation 147.1

2 Cl2 (g) → 2 Cl (g) BDE 243

3a Mg (g) → Mg+1 (g) + e- IIE1 738

3b Mg+1 (g) → Mg+2 (g) + e- IIE2 1451

4 2 Cl (g) + 2e- → 2 Cl-1 (g) Electron Affinity 2(-348.6)

5 Mg+2 (g) + 2 Cl-1 (g) → MgCl2 (s) Lattice Energy -2524

Covalent Bond
• A force that bonds two atoms
together by a sharing of electrons

• Each pair of shared electrons

creates a bond

• Usually occurs between atoms of

non-metals
 SIMPLE MOLECULES
Orbital theory
Covalent bonds are formed when orbitals, each containing one electron,
overlap. This forms a region in space where an electron pair can be found;
new molecular orbitals are formed.

orbital orbital overlap of orbitals provides

containing 1 containing 1 a region in space which can
electron electron contain a pair of electrons

The greater the overlap the stronger the bond.

Co-ordinate (Dative Bonds)
E.g. Ammonium ion
 HYDROGEN

H H H H

both atoms need one electron atoms share a pair of electrons

to complete their outer shell to form a single covalent bond

DOT AND
CROSS
DIAGRAM H H H H
 AMMONIA

H H
N
H N H

H H

atom needs three each atom needs one Nitrogen can only share 3 of
electrons to complete electron to complete its 5 electrons otherwise it will
its outer shell its outer shell exceed the maximum of 8
A LONE PAIR REMAINS

H N H H N H
H H
 WATER

H H O
O
H H

atom needs two each atom needs one Oxygen can only share 2 of its
electrons to complete electron to complete 6 electrons otherwise it will
its outer shell its outer shell exceed the maximum of 8
TWO LONE PAIRS REMAIN

H O H O
H H
 OXYGEN

O O O O

each atom needs two electrons each oxygen shares 2 of its

to complete its outer shell electrons to form a
DOUBLE COVALENT BOND

O O
 METHANE

H
H H

C H C H

H H H
atom needs four each atom needs one Carbon shares all 4 of its
electrons to complete electron to complete electrons to form 4 single
its outer shell its outer shell covalent bonds

H H
DOT AND
CROSS
DIAGRAM
H C H H C H
H H
Covalent Bonds

 Simple and Coordinate Covalent

 Defined by: BL, BA and BE
 Sigma and Pi Bonds
A covalent bond is formed when
atoms share electrons
SHARING IS
CARING!
 COVALENT BONDS
 Unlike ionic bonds with transferred electrons, covalent
bonds __________ electrons.

IONIC BOND COVALENT BOND

Multiple Bonding
 Sometimes, atoms share more than one
electron.
 Occasionally, they can share 2 or even 3
electrons.
 These are called double and triple bonds.
Plot of potential energy versus distance for two hydrogen atoms
Rule of Octet
• Atoms will combine to form compounds in order
to reach eight electrons in their outer energy
level.

o Atoms with less than 4 electrons tend to lose

electrons.

o Atoms with more than 4 electrons tend to

gain electrons.

Be aware that there are some exceptions!

 H2CO
Double and triple bonds are commonly
observed for C, N, P, O, and S

SO3

O C O
• •
• •
C2F4 •• ••

35
Violations of the Octet Rule

BF3
SF4
36
 COVALENT BONDS
 Unlike ionic bonds that generally form between metals
and nonmetals, covalent bonds form between
________________.
 Classify the bonds as ionic or covalent
1. Na-Cl
2. H-O
3. C-O
4. Ca-F
5. N-N
6. Cr-S
 More Exercises
 Use electron dot diagrams to model molecules

1. H2

2. H2O

3. NH3

4. Cl2
 COVALENT BONDING

Definition consists of a shared pair of electrons with one electron being

supplied by each atom either side of the bond.
compare this with dative covalent bonding

+ +

Formation between atoms of the same element N2, O2, diamond,

graphite

between atoms of different elements CO2, SO2

on the RHS of the table;

when one of the elements is in the CCl4, SiCl4

middle of the table;

with head-of-the-group elements BeCl2

with high ionisation energies;
 8A
1A Valence Electrons

2A 3A 4A 5A 6A 7A

Number of valence electrons is

equal to the Group number.
Polarity
 Bond Polarity

 Difference in electronegativity between

two atoms in a chemical bond
 Unequal sharing of electrons between elements
Polar and Non-Polar
Covalent Bond and
Dipole Moment

C2F4
Electronegativity values of Elements

Copyright © Houghton Mifflin 12-43

Company
Polarity of Molecules
 Dipole moment,  the magnitude of the net bond dipole of a
molecule 
 A polar bond forms due to different electronegativities.
 Most electronegative substance will have a slight negative

charge (represented as )

 The positive (electron poor) side of the bond is represented

as + or
  points in direction of the negative charge.

 Net polarity (dipole moment) of a molecule is obtained using the

vector sum of polarities of individual bonds.
 E.g. determine if NH3, H2O, CO2 have dipole moments.
 E.g.2 determine if either the cis- or trans- isomer of C2H2Cl2
Polar Covalent bond
 Electrons are shared, but not
equally.

 Some atoms have a stronger pull for

the electrons.

 Moleculenot symmetrical in shape

(unbalanced).
Polar Covalent bond
Non-Polar Covalent Bond
Example:
The hydrogen atoms are sharing two
electrons between themselves. Such a
shared pair of electrons makes up a single
bond.

HA + HB HA HB
 Sigma Bonds

- A bond symmetrical around the axis connecting two atomic

nuclei, a sigma bond is formed.
 Greek letter sigma (σ).

Bond
axis
s atomic s atomic
orbital orbital Sigma-bonding
molecular orbital
Pi Bonds
As shown here, the side-by-side overlap
of atomic p orbitals produces what are
called pi molecular orbitals. - Pi bond (𝛑)

p atomic p atomic Pi-bonding

orbital orbital molecular orbital
Drawing Lewis Structure
Examples: 1. CCl4 2. CO32- 3. ICl4-
 Sulfur Dioxide, SO2
Equivalent structures
bring in OR bring in
left pair right pair called:
RESONANCE
•• •• ••

O S O
• •
• •

••
••

••
••

•• ••
STRUCTURES
O S O
•
O S O
• • •
• • • • The proper Lewis structure
•• •• •• ••
is a HYBRID of the two.

A BETTER representation of SO2

is made by forming 2 double bonds
Each atom has
O=S=O - OCTET
- formal charge = 0

53
 Formal Atom Charges
 Atoms in molecules often bear a charge (+ or -).

Formal charge = Valence Electrons

- 1/2 (no. bond electrons)
- (no. of LP electrons)

• The most important dominant resonance structure

of a molecule is the one with formal charges
as close to zero as possible.

54
 Properties of SIMPLE COVALENT MOLECULES
Bonding Atoms are joined together within the molecule by covalent bonds.

Electrical Don’t conduct electricity as they have no mobile ions or electrons

Solubility Tend to be more soluble in organic solvents than in water;

some are hydrolysed

Boiling point Low - intermolecular forces are weak;

they increase as molecules get a larger surface area

e.g. CH4 -161°C C2H6 - 88°C C3H8 -42°C

as the intermolecular forces are weak, little energy is required to

to separate molecules from each other so boiling points are low

some boiling points are higher than expected for a given mass
because you can get additional forces of attraction
 Properties of Covalent compounds
 EXAMPLES OF COVALENT COMPOUNDS
 water
 plastic
 sugar
 Gasoline, oils & fats
 CHARACTERISTICS OF COVALENT COMPOUNDS
1. Do NOT conduct an electrical current
2. Low melting and boiling points
3. Lightweight molecules: generally gases and liquids @RT
4. Heavier molecules: generally solids at room temp
 Summary COVALENT COMPOUNDS
• When atoms share electrons, they don’t always
share them equally.
• Nonpolar covalent compounds: share e-
equally
• Will not conduct an electrical current at all
• All diatomic molecules are nonpolar
• Polar covalent compounds: share e-
unequally
Metallic Bonding

 The “sea of electrons” produces an attractive

force that fixes the positions of the metallic
ions. Because the electrons can move about
freely, metals are good conductors of heat
and electricity.
Metallic Bonding

 Metals consist of a crystalline lattice in which

positive ions are arranged in fixed patterns,
and the valence electrons are free to move.
These electrons do not belong to individual
atoms, but rather to the crystal as a whole.
 CHARACTERISTICS OF METALS

1. Malleable & ductile

2. Good conductors
 “sea of electrons” allows metals to

be shaped without breaking

 Close metal atoms have overlapping outer E levels

3. Valence electrons can move freely between positive

metal ions
Class Exercise
Exercise Draw the Correct Lewis Structure

 1. Nitric oxide, NO
 2. Formate ion, HCO2-
 3. Thiocyanate ion, (SCN) –

 4. Urea, (NH2)2CO
 5. Nitrosyl chloride, NOCl
 6. Cyanogen Flouride, FCN
Examples
Draw the correct structure:

 1. ICl4-, NH4+ and SiH4

 2. NO3-, NO+1 and CHO2-1

 3. CO, NO and OF2
 4. HCN, HCCH and HCOOH
 5. XeF2, XeF4 and XeF6
Writing Lewis structures
Steps:
(1)Count total number of valence electrons (including
charge).
(2)Draw symbols for each atom, placing the least
electronegative atom (or carbon, or the unique atom)
in the center.
(3) Connect each atom with a single bond at a cost of
2 ve- each.
(4) Distribute remaining ve- as lone pairs around the
outermost
atoms to give each an octet.
H
(5) Place1.90
any 2.20
remaining ve- on the
SiH4 | central atom.
(6) If the central atom doesn’tH have
– Si – an octet, create
#ve- = 4 + (4x1) = 8 H |
multiple
H
Exercises - #1
1. Draw Lewis structures for these:
CHO2-1 1
0
NO+1
OF2 ..
O
..
20
5
5
3.
2.

H
2.

-1
CHO2 C ..
#ve- = 4 + 1 + (2x6) + 1 = 18 O :
..
0
5
3.
3.

NO+1
#ve- = 5 + 6 - 1 = 10 :N :
O

.. .. ..
5
0
3.
4.

OF2 :F
.. .. O ..:
#ve- = 6 + (2x7) = 20 F
#2.
Both carbon monoxide and carbon dioxide are
produced by combustion of fossil fuels. Draw their 1
2
Lewis structures.
5

..
5
2.
3.

CO :C .. :O
#ve- = 4 + 6 = 10

CO2 .. ..
#ve- = 4 + (2x6) = 16 :O
.. C ..: O
#3) Odd-electron molecules
Molecules with an odd number of electrons are called
free radicals.

Example: nitric oxide (NO) 1

3

NO . ..
:N .. O
#ve- = 5 + 6
= 11
#5
Write the Lewis structures for XeF2, XeF4, XeF6
1
identify any exceptions to the octet rule. 8

XeF2 .. .. .. ..
:..
F :
#ve- = 8 + (2x7) ..Xe ..
= 22 F
..
:F:
XeF4 .. | .. ..
#ve- = 8 + (4x7) :F . Xe :
.. . ..
= 36 F |
:..
F: ..
.. :F: ..
XeF6 :..
F F..:
#ve- = 8 + (6x7) = Xe

..
50
..: :F: : ..
:F F:
..
xceptions to the octet rule
Chemistry is a field full of exceptions. There are three
types of exceptions to the octet rule.

(1)Molecules with an odd number of valence electrons

(an unpaired electron).

(2) Molecules whose central atom has less than an

octet.
(3) Hypervalent molecules whose central atom has
more than an
octet.
#6) Hypervalent molecules
Elements below the second row of the periodic table
can accommodate more than an octet using d orbitals.

Example: phosphorus pentachloride (PCl5) 1

.. 6
:Cl:
PCl5 .. ..
#ve- = 5 + (5x7) :Cl
.. P .. :
= 40 ..
Cl
:Cl : Cl:
.. ..
Example: sulfur hexafluoride (SF6).. 1
7
.. :F: ..
SF6 :..
F F..:
#ve- = 6 + (6x7) = S
48
..: :F: : ..
:F F:
..
 #7
NASA’s Cassini-Huygens mission detected a cloud of
toxic hydrogen cyanide (HCN) on Titan, one of Saturn’s
moons. Titan’s atmosphere also includes ethane
(H3CCH3), acetylene (HCCH) and ammonia (NH3). 11
Draw their Lewis structures! NH3
#ve- = 5+ (3x1) = 8
2
3. 5
o
2.
2.

HCN H C : N
#ve- = 1+ 4 + 5 = 10 ..
N
H H H H
H3CCH3 H
#ve- = (6x1) + (2x4) = 14
H |C | C
H | |
H H

HCCH H C C
#ve- = (2x1) + (2x4) = 10 H
Theories of Chemical Bonding
VSEPR Theory
In order to explain the three-dimensional
shape of molecules, scientists use valence-
shell electron-pair repulsion theory (VSEPR
theory).

 VSEPR theory states that the repulsion

between electron pairs causes molecular
shapes to adjust so that the valence-electron
pairs stay as far apart as possible.
VSEPR
 Valence Shell Electron Pair Repulsion
Theory
1. Shared and unshared pairs repel.
2. Lone pairs repel stronger than shared pairs.
3. Double and triple bonds are viewed as single;
for structure only.
4. The resultant shape of the molecule is a result
of shared and lone pairs being as far apart as
possible.
Bonding and Shape of
Molecules
Number Number of Covalent
of Bonds Unshared Pairs Structure Shape Examples

2 0 -Be- Linear BeCl2

B
3 0 Trigonal planar BF3

4 0 C Tetrahedral CH4, SiCl4

:

3 1 N Pyramidal NH3, PCl3

:

2 2 O: Bent
H2O, H2S, SCl2
 VSEPR Theory
Here are some common molecular shapes.

Linear Trigonal planar Bent Pyramidal

Tetrahedral Trigonal Octahedral Square

bipyramidal planar
Valence Share Electron Pair
Repulsion (VSEPR) Theory
 Valence Share Electron-Pair Repulsion (VSEPR)
model allows us to predict the molecular shape by
assuming that the repulsive forces of electron pairs
cause them to be as far apart as possible from each
other.
 Only the valence electron pairs are considered in

determining the geometry.

 Review: valence electrons are the additional

electrons in an atom beyond the inert gas core; for

the neutral atom the number is equal to the group
number, i.e. C has 4, N has 5, O has 6, and F has 7.
Molecular structure of methane.

12-80
Steps

1. Draw the Lewis structure of a compound.

2. Count the # bonds and lone pairs.

3. Apply the VSEPR rules for shape.

Table of Shapes
# Pair # Lone Molecular Shape Bond
Groups Pairs Angles
2 0 Linear 180o

3 0 Trigonal planar 120o

1 Bent <120o
4 0 Tetrahedron 109.5o
1 Trigonal pyramid <107o
2 Bent <105o
Molecular Geometry Diagram Description Example

Linear(AX2) 2 outside atoms CO2

0 lone pairs

Bent (AX2) 2 outside atoms H2O

2 lone pairs

trigonal planar 3 outside atoms BF3

0 lone pairs
(AX3, A = boron)

Tetrahedral (AX4) 4 outside atoms CH4

0 lone pairs

trigonal 3 outside atoms NH3

pyramidal (AX3) 1 lone pair
 “Molecular Geometry”
Complete the following table for each molecule or ion

Molecule Lewis Structure Bonding Nonbonding Approx. 3-D Sketch Molecular Polar or
or Ion Electron Electron Bond Shape Nonpolar
Pairs Pairs Angle Molecule

CH4 H 4 0 109.5 H tetrahedral nonpolar

H-C-H C
H H
H
H

Multiple bonds are unidirectional and

count as one area of electron density
Geometry with No Lone Pairs

2 charge clouds, 3 charge clouds, 4 charge clouds,

linear trigonal planar tetrahedral

5 charge clouds, 6 charge clouds,

trigonal bipyramidal Octahedral
Molecular Shapes
Examples
Planar vs. Pyramidal
 Both have similar formula (AX3)

 Look at the central atom

 If it has unbonded electrons, it

will be trigonal pyramidal

 If it doesn’t have unbonded No unbonded
electrons (only boron!), it will Electrons on boron
be trigonal planar
Trigonal Planar

 Boron is central atom surrounded by three

fluorine atoms (or H or other halogen)
 Boron can defy octet rule, happy with six
electrons
 No unbonded electrons on boron, fluorine atoms
stay within a single plane
 Write all

Trigonal Pyramidal

 Nitrogen surrounded by three hydrogen atoms (or

halogens)
 One pair of unbonded electrons, push hydrogens out of

plane

http://dl.clackamas.edu/ch104/lesson9images/molecshapes4.jpg
 Bent vs. Linear
What’s The Difference?
 Both have a similar
Unbonded electrons formula (AX2)
on oxygen  Look at the central atom No unbonded electrons
on carbon
 If the element is group 14,

it is linear

 If the element is group 16, Linear

Bent it is bent

 Look for presence or

absence of unbonded
electrons
Bent

 Oxygen is central atom

 Central atom is typically group 16.
 Surrounded by two atoms (H or halogen)
 Two unbonded electron pairs on oxygen, push

hydrogens out of the plane

Linear

 Carbon is central atom

 Surrounded by two oxygen atoms
 No unbonded electrons on carbon
 Look for AX2 geometry
 Central atom is group 14
Tetrahedral

 AX4 formula
 Carbon (or silicon) surrounded by four hydrogens (or
halogens)
 Only shape we’re concerned with four surrounding atoms
Determine the Geometry

 1. SO42-

 2. NH3

 3. SF4

 4. PCl3

 5. SO3
Hybridization
Valence Bond Theory - VBT

 Overlap of Orbitals
 Simple VBT is applicable for simple
molecules like: H2, HF, H2O and NH3
 But completely fails to explains the
formation of CH4
VALENCE BOND THEORY (VBT)
 Valence Bond Theory: a quantum mechanical
description of bonding that pictures covalent bond
formation as the overlap of two singly occupied
atomic orbitals.
 VSEPR effective but ignores the orbital concepts
discussed in quantum mechanics.
 CH4:The 1s orbital of hydrogen must overlap with the
2s and 2p orbitals of carbon.
 By constructive interference – new waves result.
 The s and p orbitals around an atom such as carbon
become equivalent and the orbitals become a hybrid
(sp3) of the original orbitals.
 Hybrid orbitals are as far apart as possible.
Hybridization - Principles
 - HOs are strongly directional and form stronger bonds
that the pure AOs
 - Number of Hos = Number of AOs mixed
 - One lobe is large (constructive) and the other lobe
(destructive) interference of waves
 - The sigma bonds and lone pairs take part in
hybridization but not the pi – bonds
 - Type of Hybridization of an element in a cpd
The sp hybrid atomic orbitals
 The sp hybrid atomic orbitals are possible
states of electron in an atom, especially when
it is bonded to others. These electron states
have half 2s and half 2p characters
sp2 hybrid orbitals
 When the central
atom makes use of
sp2 hybridized
orbitals, the
compound so formed
has a trigonal shape.
BF3 is such a
molecule:
sp3 hybrid orbitals
 Mixing one s and all three
p atomic orbitals
produces a set of four
equivalent sp3 hybrid
atomic orbitals. The four
sp3 hybrid orbitals points
towards the vertices of a
tetrahedron, as shown
here in this photograph
 Inthe case of methane, the three 2p orbitals
of the carbon atom are combined with its 2s
orbital to form four new orbitals called "sp3"
hybrid orbitals.
.
Hybridization Involving Multiple
Bonds
 Onlya maximum of two electrons can occupy
any orbital whether it is an atomic orbital or a
molecular orbital due to electron-electron
repulsion.
σ and π bonds
Looking at information comparing σ and π bonds, we
can see that double bonds are stronger than single
bonds, but not twice as strong. This is because the
sideways overlap (π bond) is weaker than the end-on
overlap (σ bond).
Bonding Mean
Bond type orbitals Bond length bond enthalpy
present
C C 1σ 154 pm 370 kJ mol–1

C C 1σ+1π 134 pm 602 kJ mol–1

C C 1σ+2π 121 pm 835 kJ mol–1

Atomic orbitals (AO) Linearly Combined Atomic Orbitals
(LCAO)
linear

sp
2s 2py
trigonal
plane

2s 2py 2px sp2

+ + +

2s 2py 2px 2pz sp3 tetrahedral

Hybridization

109
 Question
The hybridization of the central nitrogen atom in the
N2O molecule is

a) sp
b) sp2
c) sp3
d) dsp3
e) The hybridization can vary depending on the
chosen resonance structure of the molecule. 110
Exercise
Determine the Hybridization of the central element
 A – SO2

 B – PCl5

 C – SF6

 D – XeF6

 E – ICl6-
Molecular Orbital theory - MOT
Molecular Orbital Theory
 Electrons go into the lowest energy orbital
available to form lowest potential energy for
the molecule.
 The maximum number of electrons in each
molecular orbital is two. (Pauli exclusion
principle)
 One electron goes into orbitals of equal
energy, with parallel spin, before they begin
to pair up. (Hund's Rule.)
MO Theory of Bonding
 Molecular Orbital Theory extends quantum theory and states
that electrons spread throughout the molecule in molecular
orbitals = region in a molecule in which an electron is likely to
be which is similar to the concept discussed in quantum theory.
Molecular orbitals are considered to be the result of the
combination of atomic orbitals.

 Hydrogen: when two atomic orbitals from hydrogen approach

each other they form 2 molecular orbitals,  and *, bonding
orbital and antibonding orbital respectively.
 The energy of the bonding orbital is lower than the original atomic
orbital.
 The energy of the antibonding orbital is higher than the original
atomic orbitals and thus destabilizes the molecule.  *
 The electron distribution of H2 would be: 1s  , * 1s . An
excited state of this molecule would be 1s  ,  2s  .
Molecular Orbital Diagram (H2)

http://www.ch.ic.ac.uk/vchemlib/course/mo_theory/main.html
MOT of Diatomic Molecules

 2
He2: 1s 2 1*s  no net stabilization (or
bonding).

He 21s 1s 
1
  2 *  a net of one bonding electron.

 Bond order: BO = 1/2(nb  na) where nb is the

number of bonding electrons and na is the number
of antibonding electrons.
E.g. For He2 BO(He2) = 1/2(2 2) = 0.
E.g.2 H2 on the other hand would have a BO(H2) =
1/2(2  0) = 1 or there is a single bond between the
two atoms. 1
2 *
  2
 Li : 1s  1s  2s   BO=1/2(4  2) = 1.
2



1s 2 of
Molecule
O:
2
1*slithium 2s  2p 4 2p 2 *2p 
2 * 2be stable.
2s should
2
;
2

BO= 1/2(10  6) = 2. Last two filled orbitals are Fig. 10.34 MO Diagram of
antibonding  one elctron in each orbital (Hund’s
rule) or two unpaired electrons  O2 a N2
paramagnetic molecule.
MO Diagram for O2

http://www.chem.uncc.edu/faculty/murphy/1251/slides/C19b/sld027.htm
 MO Levels of 2nd Row Elements
Large 2s-2p interaction Small 2s-2p interaction

B2 C2 N2 O2 F2 Ne2
*2p 
*2p      
2p    
2p
           
*2s      
 2s      
Bond Order 1 2 3 2 1 0
Magnetic behavior P D D P D

P = Paramagnetic; D = Diamagnetic
Chapter 10-118
Conclusions
 Bonding electrons are localized between
atoms (or are lone pairs).
 Atomic orbitals overlap to form bonds.
 Two electrons of opposite spin can occupy
the overlapping orbitals.
 Bonding increases the probability of finding
electrons in between atoms.
 It is also possible for atoms to form ionic and
metallic bonds.
Exercise
 Determine the Bond Order
 A. O2=
 B. O2-
 C. O2+
 D. NO
 E. CO
Solids:
 Crystalline
- regular
 Amorphous - random

Types
1. Ionic

2. Covalent

3. Metallic
Examples
4. Molecular
1. NaCl, CaCl
2
2. Diamond, Silica
3. Silver, Copper

4. Ice, dry CO

2
Thank You !!!