CHAPTER 4

Chemical
bonds
CHEMICAL BOND
 When two or more
atoms attach to
each other, they
form a chemical
bond.
 Chemical bond is a
strong attractive
force that exists
between atoms in a
substance.
 Electrons are
responsible for the
type, strength, and
size of a chemical
bond 2
 Has a significant effect on chemical and
physical properties of compounds
 Involves the valence electrons

Valence Electrons – the electrons

in the outermost energy level of
an atom
-

This Lithium +
Atom has one - + +
-

valence
electron

3
COUNTING VALENCE ELECTRONS

- - -
-

-
-

+
+ ++ + +
+ + +
-
+
+ -
- - -
+ + -

+
+ + +
+
- -
-

- -
-

Carbon Oxygen Beryllium

4 6 2 valence
valence valence electrons
electrons
electrons 4
DETERMINING THE NUMBER OF
VALENCE ELECTRONS BY USING THE
PERIODIC TABLE

* Atoms of elements in Group 3-12 typically 5

have between 1 or 2 valence electrons.

HOW MANY VALENCE ELECTRONS?
 Electrons are divided between core and
valence electrons.

ATOM core valenc

e
Na 1s2 2s2 2p6 3s1 1s2 2s2 2p6 3s1
Br 1s2 2s2 2p6 3s2 3p6 1s2 2s2 2p6 3s2 3p6 4s2 4p5
4s2 3d10 4p5 3d10

6
 CHEMICAL BONDING
 In chemical
bonds,
atoms can
either
 transferor
 share their
valence
electrons.

7
 Four types of chemical bonds:
 Ionicbond or electrovalent bond
 Covalent bond
 Dative covalent bond or coordinate covalent
bond
 Metallic bond

 Two types of intermolecular forces

 VanDer Waals forces
 Hydrogen bonding

8
NOBLE GASES AND OCTET STABILITY
 Noble gases are unlike
any other group of
elements on the periodic
table because of their
extreme stability.
 Each noble gas has eight
valence electrons, except
for helium, which has two.
 Atoms can become stable
by having eight electrons
in their outer energy
level, as shown in the
noble gas, for example
Neon, (or two electrons in 9
the case of some of the
smallest atoms).
 REPRESENTATION OF ATOMS: LEWIS
SYMBOLS
 Representing atoms
by showing only the
valance electrons
 Electrons (valance) are

represented as dots
around the chemical
symbol of the atom
 Dots can be placed on

the 4 sides of the Each unpaired dot is available

chemical symbol – for bonding with other atoms
place one electron
each side, then start
to add remaining
electrons
LEWIS STRUCTURE
 The Lewis structure is a simple two-
dimensional representation of the positions
of electron pairs around a central atom of a
molecule.
 Valence electrons are distributed as:
 bond pairs (BP) (bonding electrons)
 lone pairs (LP) (non bonding electrons)

H Cl 1 lone pairs (LP) = 2 non bonding

electrons

1 bond pairs (BP) = 2 bonding electrons 11

DRAWING A LEWIS STRUCTURE
1. Identify the central atom in the molecule.
 The central atom is the least electronegative atom in the molecule
or atom that requires the most number of electrons to complete an
octet.
2. Calculate the total number of valence electrons of the
molecule by adding up the number of valence electrons for
each atom.
3. Write the skeletal structure for the molecule.
 The Lewis structure of a molecule must have the atoms in the
correct positions.
4. Distribute electrons to the atoms surrounding the central
atom such that the octet rule of all the surrounding atoms is
satisfied.
 Begin by placing 2 electrons between each pair of atoms. Then,
distribute the remaining electrons, first to terminal atoms, and then
to the central atom, giving octets to as many atoms as possible.
5. If any atoms lack an octet, form double or triple bonds as
necessary to give them octet.
 To obtain a multiple bond, move one or two electron pairs
(depending on whether the bond is to be double or triple)
from a surrounding atom to the bond connecting the central atom.
Atoms that usually form multiple bonds are C, N, O, and S.

12
 No of valence electrons = group
number
REMEMBER!!! group 1A – 4A(14) ,
no. of bond pairs = group number
group 5A (15) – 7A (17),
no of bond pairs = 8 – group number
* Except for H
Ato Number of Lone pairs of
m bond pair electron
4 bonds
C 4 0 C C C C

N 3 1 N N N 3 bonds

O O 2 bonds
O 2 2

Cl 1 bond
F 1 3
13
H 1 bond
H 1 0
 Write the Lewis structure of nitrogen trifluoride (NF3)
Step 1 – N is less electronegative than F, put N in center

Step 2 – Count valence electrons N = 5 (2s22p3) and F = 7 (2s22p5)

N = 5 e-
F = (3 x 7) = 21 e-
Total = 26 valence electrons

Step 3 – Draw single bonds between N and F atoms and complete

octets on N and F atoms.

Step 4 - Check, are sum of e- in structure equal to number of valence e-?

3 single bonds (3x2) + 10 lone pairs (10x2) = 26 valence electrons

F N F

14
F
Write the Lewis structure of the carbonate ion (CO32-).

Step 1 – C is less electronegative than O, put C in center

Step 2 – Count valence electrons C = 4 (2s22p2) and O = 6 (2s22p4)
-2 charge – 2e-
‘add’ for negative charge
4 + (3 x 6) + 2 = 24 valence electrons ‘minus’ for positive charge
Step 3 – Draw single bonds between C and O atoms and complete
octet on C and O atoms.
Step 4 - Check, are sum of e- in structure equal to number of valence e- ?

Step 5 - Too many electrons, form double bond and re-check sum of e-

2- 2 single bonds (2x2) = 4

1 double bond = 4
O C O 8 lone pairs (8x2) = 16
Total = 24 15
O
FORMAL CHARGE
 The charge assigned to an atom in
a molecule, assuming that electrons in all
chemical bonds are shared equally between
atoms, regardless of
relative electronegativity.

 When determining the best Lewis

structure (or predominant resonance
structure) for a molecule, the structure is
chosen such that the formal charge on each
of the atoms is as close to zero as possible.
16
17
EXAMPLE 1

18
EXAMPLE 2

19
OCTET RULE
 Octet rule; atoms react in such a way that
they have eight electrons in their valance
(outermost) shell (more stable configuration).
 This configuration of 8 electrons in the

valance shell is also known as “noble gas

configuration”
 Noble gases (group 8A) are not reactive,

since they have their valance shells already

filled with 8 electrons (Helium is an exception
and has 2 electrons in its only shell).

20
 Other atoms lose/gain or share electrons to
achieve the more stable noble gas
configuration.

 By using octet rule, we can predict the

chemical changes between atoms. 21
 EXCEPTIONS TO THE OCTET RULE
Group of molecules with a central
The Incomplete Octet atom having fewer than 8 ēs
around it.
BeH2 Be – 2e- H Be H
2H – 2x1e-
4e-

B – 3e- 3 single bonds (3x2) = 6

3F – 3x7e- F B F
BF3 9 lone pairs (9x2) = 18
24e- Total = 24
F
22
The Expanded Octet (central atom with principal quantum number n > 2)
Group of molecules with a central atom having more than 8 ēs
around it
SF6 S – 6e- F 6 single bonds (6x2) = 12
6F – 42e- F F 18 lone pairs (18x2) = 36
48e- S Total = 48

F F
F

23
CHEMICAL BOND FORMATION
 Three important types of chemical
bonding:
1) In a “covalent bond” one or more pairs of
electrons are shared equally between the
atoms
2) In an “ionic bond” electrons are totally
transferred from one atom to another
3) In a “dative covalent bond” one atom
donates a lone pair of electrons to another
atom
COVALENT BOND: SHARING OF
ELECTRONS
 In covalent bonding
electrons are shared between
atoms
 The two orbitals with the
valance electrons should
overlap for covalent bond
formation
 This way the atoms sharing
electrons gain full valance
shell – more stable (octet rule)
 Atoms which are linked by
covalent bonds form discrete
units called molecules; the
smallest part of a single
element (O2) or a compound
(such as glucose, C6H12O6)
 The molecular formula show
the composition of one
molecule of a covalent
compound
 COVALENT BONDS: SINGLE AND MULTIPLE
BONDS

 Types of covalent
bonds: Sigma (σ) and
pi (π) bonds
 Single or multiple
bonds can form
between two atoms
 Single bonds are
always sigma bonds

Single bond – one sigma bond

Double bond – one sigma bond + one pi bond
Triple bond – one sigma bond + 2 pi bonds
MULTIPLE BONDS IN COVALENT
BONDING
 Different covalent bond types share a
different number of electrons
Water (H2O) Carbon Dioxide (CO2) Nitrogen (N2)
- -
- - - -
- - - -
-
-
-
- -
++ +
-
- -
++ +
- + + + - ++ ++ ++
++ + - - - - + + + - - + + +
- + + + + + + +
- + + + + - - - - + + + +
+ + + +
+ + - -
- -
- -
- -

- - - -
- -

Single Double Bonds Triple Bonds

Bonds Share Share 4 Share 6
2 Electrons Electrons Electrons 27
RESONANCE
 The two shared electron pairs
constitute a double bond.
 The double bond can be placed

between the sulfur and any of the three

oxygen atoms. The structural formula can be
shown as any of the structures below. This
phenomenon is called resonance.

28
PROPERTIES OF COVALENT
COMPOUNDS
 Gases, liquids and solids at room
temperature
 May be hard or soft (diamond is a covalent

solid)
 Dissolve in polar and non-polar solvents,

depending on molecule’s polarity

 Solutions and melts do not conduct
electricity
 Most covalent compounds are molecular

29
 IONIC BOND: TRANSFER OF
ELECTRONS
 Ionic bonds are formed when
one or more electrons are fully
transferred from one atom to
another – one atom becomes
positively charged (cation)
another becomes negatively
charged (anion)
 The attraction between the
oppositely charged cations and
anions makes the the ‘ionic
bond’ between the ions -
electrostatic interaction
 Ionic compounds exist as
extended lattices–a network of
cations and anions
 Ionic compunds have an overall
charge of zero due to equal
number of positive and negative
charges within the compound
EXERCISES
 Draw Lewis structure for the formation of
following ionic compounds.
a. CaBr2
b. PbO

31
PROPERTIES OF IONIC COMPOUNDS
 Hard, rigid solids at room temperature
 High melting and boiling point

 Dissolve in polar solvents (if soluble)

 Solutions conduct electricity

 Melts conduct electricity

 Closely packed dense structures

32
DATIVE / COORDINATE COVALENT
BONDS
 A covalent bond resulting from one atom
donating a lone pair of electrons to another atom
is called a dative or coordinate covalent
bond.
 A good example of a molecule with a coordinate
covalent bond is ozone, O3.

33
EXAMPLE
 Hydroxonium ion, H3O+

34
EXERCISES
 Draw Lewis structure for the formation of
following covalent compounds and
polyatomic ions.
a. NH3
b. CH4
c. C2H6
d. CO32-
e. NH4+

35
VALENCE SHELL ELECTRON PAIR
REPULSION (VSEPR) THEORY
 It is a method for predicting the shape of a
molecule from the knowledge of the groups
of electrons around a central atom.

36
MOLECULAR SHAPE
 VSEPR theory assumes that
the shape of a molecule is
determined by the repulsion
of electron pairs.
 This theory states that all
bonding pairs of electrons
and lone pairs of electron in
the valence shell of the
central atom repel one
another and tend to be as
far away as possible so as to
minimise the repulsions
DETERMINING MOLECULAR SHAPE
 The central atom is called A.
 All the outer atoms are designated with an X.

 Any lone pair electrons are designated with

an E.
 MOLECULES WITH ONLY
PAIRED ELECTRONS
AROUND THE CENTRAL
ATOM.
39
LINEAR
• 2 atoms attached to center atom
• 0 unshared pairs (lone pairs)

• Bond angle = 180o

• Type: AX2
• Ex. : CO2 BeF2,
TRIGONAL PLANAR
• 3 atoms attached to center atom
• 0 lone pairs

• Bond angle = 120o

• Type: AX3
• Ex. : BF3
TETRAHEDRAL
• 4 atoms attached to center
atom
• 0 lone pairs

• Bond angle = 109.5o

• Type: AX4 109.5°

• Ex. : CH4, CCl4

Bonds are all evenly spaced electrons

TRIGONAL BIPYRAMIDAL
• 5 atoms attached to center atom
• 0 lone pairs

• Bond angle =
– equatorial -> 120o
– axial -> 90o

• Type: AX5
• Ex. : PF5
OCTAHEDRAL
• 6 atoms attached to center atom
• 0 lone pairs

• Bond angle = 90o

• Type: AX6
• Ex. : SF6
 MOLECULES WITH BOTH
PAIRED AND UNSHARED
(LONE) PAIRS OF
ELECTRONS AROUND THE
CENTRAL ATOM.
45
BENT
• 2 atoms attached to center
atom
• 2 lone pairs

• Bond angle = 104.5o

• Type: AX2E2
• Ex. : H2O
104.5°
2 unshared pairs of e’s at top of O repel bonds and
force them to bend
TRIGONAL PYRAMIDAL
• 3 atoms attached to center atom
• 1 lone pair

• Bond angle = 107o

• Type: AX3E
• Ex. : NH3

Less repulsion between the bonding pairs of electrons

EXAMPLE: PREDICT THE SHAPE OF CO2,
AND HCN BY USING VSEPR THEORY.
EXAMPLE: PREDICT THE SHAPE OF CH4, NH3
AND H2O BY USING VSEPR THEORY.
BOND POLARITY AND DIPOLE
MOMENT
 Bond polarity
 e.g.,HF molecule. F is more electronegative than
H, so there is partial charge separation in the H-
F bond:

 theH-F bond is described as “polar covalent

bond” and is said to have a “dipole moment”
 A dipole moment results when a polar
molecule has a center for positive charge
separate from a center for negative charge.
 Water molecule dipole moment

54
MOLECULE POLARITY
 Polar bonds do not always mean the molecule is polar.
 In very symmetrical structures (e.g., CO2 or CF4), the
individual bond dipoles effectively cancel each other
and the molecule is non-polar.

 In less symmetrical structures (e.g., SO2 and SF4), the

bond dipoles do not cancel and there is a net dipole
moment which makes the molecule polar.

rizanayusof_201
 Distribution of polar bonds around the central atoms
Symmetric Asymmetric
Non-polar polar

O
H H
Symmetric
Non-polar
Symmetric
Non-polar
Cl

C
Cl
Cl Cl
Asymmetric
polar 56
INTERMOLECULAR FORCES IN
COVALENT BOND
 Intermolecular interactions are weak
interactions between molecules.
 These interactions determine physical

properties such as boiling point, melting

point, density etc.
 Although they are weak, multiple interactions

occur at the same time between two

molecules to give a large overall effect.

57
TYPES OF INTERMOLECULAR FORCES
IN COVALENT BOND
 Hydrogen bonding
A hydrogen atom
covalently bound to an
oxygen (O), nitrogen (N) or
fluorine (F) atom can
interact with an unshared
electron pair on another
oxygen, nitrogen or
fluorine atom to form a
hydrogen bond.
 Hydrogen bonds are
relatively weak compared
to covalent bonds, but
58
stronger than Van der
Waals interactions.
 Van der Waals forces
 Opposite charges attract, like charges repel
 Due to polar covalent bonds – one part of the
molecule has partial negative and one part has
partial positive charge – these molecules are said
to have dipole
 Ion-dipole forces, dispersion forces and dipole-
dipole interactions are types of Van der Waals
forces.
 The strength of van der Waals forces increases
with an increase in molar mass or molecular size.

59
EFFECT OF INTERMOLECULAR FORCES ON
CHANGING OF THE THREE STATES OF
MATTER
 The extent of intermolecular
interactions between
molecules determines the
physical state of a
substance; solid, liquid, gas.
 Solid > liquid > gas (the
order of the strength of
intermolecular interactions)
 The physical state of a
substance can be changed
by altering the number of
interactions between its
molecules; this is achieved
by giving or taking energy
from the substance –
generally by heat energy
THREE STATES OF MATTER
 As we increase the energy of a substance, its molecules
exhibit greater degree of movement and finally overcome
the attractive forces holding the molecules together
 Polar molecules have higher melting and boiling points, non-
polar molecules have lower melting and boiling points
(water b.p. =100 °C vs. methane b.p.= -161 °C)