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H2 Chemistry Notes

H2 Chemistry (9729)
Lecture Notes 4
Chemical Bonding
Assessment Objectives:
Candidates should be able to:
(a) show understanding that all chemical bonds are electrostatic in nature and describe:
(i) ionic bond as the electrostatic attraction between oppositely charged ions
(ii) covalent bond as the electrostatic attraction between a shared pair of electrons and
positively charged nuclei
(iii) metallic bond as the electrostatic attraction between a lattice of positive ions and delocalised
electrons
(b) describe, including the use of ‘dot-and-cross’ diagrams,
(i) ionic bonding as in sodium chloride and magnesium oxide
(ii) covalent bonding as in hydrogen; oxygen; nitrogen; chlorine; hydrogen chloride; carbon
dioxide; methane; ethane
(iii) co-ordinate (dative covalent) bonding, as in formation of the ammonium ion and in the Al 2Cl6
molecule
(c) describe covalent bonding in terms of orbital overlap (limited to s and p orbitals only), giving σ and π
bonds
(d) explain the shapes of, and bond angles in, molecules such as BF3 (trigonal planar); CO2 (linear) CH4
(tetrahedral); NH3 (trigonal pyramidal); H2O (bent); SF6 (octahedral) by using the Valence Shell
Electron Pair Repulsion theory
(e) predict the shapes of, and bond angles in, molecules analogous to those specified in (d)
(f) explain and deduce bond polarity using the concept of electronegativity
[quantitative treatment of electronegativity is not required]
(g) deduce the polarity of a molecule using bond polarity and its molecular shape (analogous to those
specified in (d));
(h) describe the following forces of attraction (electrostatic in nature):
(i) intermolecular forces, based on permanent and induced dipoles, as in CHCl3(l); Br2(l) and
the liquid noble gases
(ii) hydrogen bonding, using ammonia and water as examples of molecules containing –NH and
–OH groups
(i) outline the importance of hydrogen bonding to the physical properties of substances, including ice
and water
(j) explain the terms bond energy and bond length for covalent bonds
(k) compare the reactivities of covalent bonds in terms of bond energy, bond length and bond polarity
(l) describe, in simple terms, the lattice structure of a crystalline solid which is:

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(i) ionic, as in sodium chloride and magnesium oxide

(ii) simple molecular, as in iodine
(iii) giant molecular, as in graphite and diamond
(iv) hydrogen-bonded, as in ice
(v) metallic, as in copper
[the concept of the ‘unit cell’ is not required]
(m) describe, interpret and/or predict the effect of different types of structure and bonding on the
physical properties of substances
(n) suggest the type of structure and bonding present in a substance from given information
Content Recommended Materials:
 Octet Rule  Cambridge International AS and A Level Chemistry by Peter
 Formation of Covalent Cann and Peter Hughes, published by Hodder Education
Bonds  A-Level Chemistry (4th Edition) by E N Ramsden, published
 Sigma and Pi Bonds by Oxford University Press
 Hybridisation  Advanced Study Guide Chemistry by C S Toh, published by

 Dative bonds Step-by-Step International Pte. Ltd.

 Exceptions to Octet Rule

 Molecular Ions
 Shapes of Molecules and
Molecular ions
 Electronegativity of
Central/Side atoms
 Covalent Bond Strength

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INTRODUCTION

The reaction of two or more elements results in the formation of a chemical bond between atoms and
hence leads to the formation of a chemical compound. The chemical bond formed between atoms results in
the formation of different types of chemical bonds. This results in different structures and different
properties of the chemical compounds formed.
1. Chemical Bonds and Octet Rule
(a) Chemical bonds are the binding forces of attraction between particles (atoms, ions or
molecules) and which result in a lower energy arrangement. The formation of a bond involves the
re-distribution of the outer electrons of the atoms concerned.
(b) The octet rule states that “atoms tend to lose, gain or share electrons until they have eight
electrons in their valence shell.”
- Atoms lose, gain or share electrons to achieve the same number of electrons as the noble
gases closest to them in the Periodic Table.
- All noble gases (with the exception of helium) have eight valence electrons. They have high
ionisation energies, low affinities for additional electrons and a general lack of reactivity.
- However, there are many exceptions to the octet rule.
2. Covalent Bonding
2.1. Formation of Covalent Bonds
A covalent bond is formed by the sharing of electrons. The shared electrons are localised between
the two nuclei.

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Covalent bonding is the electrostatic attraction between the shared electron pair and the nuclei of
both atoms.
a) Covalent bonds usually occur between non-metals. It is energetically unfavourable for non-metal
atoms to lose electrons.
b) Non-metallic compounds share electrons to form covalent bonds with each other to attain stable
octet configuration.
c) In a structural formula, each covalent bond is represented as a straight line ‘ ____’ between two atoms.
One ‘____’ represents two electrons. A structural formula shows which atoms are present in the
molecule, and how they are attached to each other.
d) There are two classes of covalent molecules
i. Giant Covalent Molecules
ii. Simple Covalent Molecules

2.2. Dot-and Cross Diagrams

Steps to drawing ‘dot-and-cross’ diagrams of ionic compounds:
i. Write down the correct chemical formula of ONE formula unit of the ionic compound e.g. Na2S
ii. Write down the symbol representing the metal, and enclose it within square brackets
iii. Determine the number of valence electrons lost from this metal atom, and write this as the
charge on the cation.
iv. Beside the completed cation, write down the symbol representing the non-metal, and use dots
to represent the correct number of valence electrons in this atom.
v. Determine the number of electron gained by this non-metal atom for it to achieve an octet
configuration, and use crosses to represent these additional electrons.
vi. Enclose the non-metal in square brackets and reflect the number of electrons gained as the
charge on the anion.
vii. Check that the respective numbers of cations / anions correspond to that in the chemical
formula of the ionic compound. Write the appropriate number as a coefficient to the square
brackets, NOT as subscripts.
Steps to drawing ‘dot-and-cross’ diagrams for species with covalent bonds:
Guiding Principle: Achieving the noble gas configuration
- When atoms form bonds, they will achieve the noble gas configuration: ns 2 np6 (8 electrons I
their outermost shell), where possible.
- So ‘dot-and-cross’ diagrams should be drawn such that the octet rule is obeyed by the maximum
number of atoms (particularly side atoms), with the exception of the H atom which can only hold
2 electrons in its valence shell.
Steps to drawing:

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i. Identify the central atom and the side atoms. The central atom is usually the less
electronegative atom.
ii. Determine the number of valence electrons of each atom.
iii. Determine the number of bonds each atom needs to form in order to achieve octet, where
possible
iv. Lone pairs of electrons (non-bonding electrons) in the valence shells of the central and side
atoms must be shown in the ‘dot-and-cross’ diagram.
Dot-and-cross diagrams for charged species:
i. For polyatomic cations, electrons are generally lost from the less electronegative atom (usually
the central atom)
ii. For polyatomic anions, electrons are generally gained by the more electronegative atom.
iii. The overall charge on the ion must be included and with square brackets drawn around the
ion.
Exercise
Note: Do not use concentric circles
a. CH4 b. CO2

3. Sigma and Pi Bonds (σ and π Bonds)

a) In forming covalent bonds, each atom must have an unpaired electron in a valence or an outer
shell atomic orbital.
b) During bond formation, two atomic orbitals, each with an unpaired electron, overlap to form a
molecular orbital containing an electron pair.
c) The overlapping of orbitals can occur in two different ways giving rise to:
i. Sigma (σ) bonds
ii. Pi (π) bonds

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3.1. Formation of Sigma (σ) Bonds

A sigma bond is formed when atomic orbitals overlap in a head-on manner.
i. s and s orbitals
Example: H-H
Two hydrogen atom: Two 1s orbitals

⇀ ⇀

ii. s and p orbitals

Example: C-H
Hydrogen atom: 1s

⇀
Carbon atom: 1s 2s 2px 2py 2pz

⇌ ⇌ ⇀ ⇀

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iii. p and p orbitals

Example: C-C
Carbon atom: 1s 2s 2px 2py 2pz

⇌ ⇌ ⇀ ⇀
Carbon atom: 1s 2s 2px 2py 2pz

⇌ ⇌ ⇀ ⇀

3.2. Formation of Pi (π) Bonds

a) A pi bond is formed when two p orbitals overlap in a side-on manner (above and below the line
drawn through the 2 nuclei).
b) A pi bond is weaker than a sigma bond due to the lower extent of the ‘side-on’ overlap compared
to the ‘head-on’ overlap.
c) Pi bonds occur in compounds containing multiple (double or triple) bonds.

i. p and p orbitals
Example: C-C
Carbon atom: 1s 2s 2px 2py 2pz

⇌ ⇌ ⇀ ⇀
Carbon atom: 1s 2s 2px 2py 2pz

⇌ ⇌ ⇀ ⇀

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Example 1: Formation of oxygen molecule, O=O

Oxygen atom: 1s 2s 2px 2py 2pz

⇌ ⇌ ⇌ ⇀ ⇀

Oxygen atom: 1s 2s 2px 2py 2pz

⇌ ⇌ ⇌ ⇀ ⇀

Head-on overlap between two 2py orbitals produces a sigma (σ) bond
Side-on overlap between two 2pz orbitals produces a pi (π) bond.

4. Hybridisation
Note: In hybridisation, we only need to consider the orbitals in the outmost quantum shell of the atoms.
- The theory of covalent bond formation via overlapping of atomic orbitals does not always give good
agreement with observations.
- Hybridisation is a concept used to explain the observed shapes of molecules (determined by
experimental studies).
- Consider the electronic configuration of carbon at ground state (1s2 2s2 2p2)
o To form a covalent bond, an orbital containing one electron is required. These orbitals overlap to form
a covalent bond.
o Carbon in its ground state contains only two singly occupied orbitals, thus it should form 2 covalent
bonds. However, we know that carbon tends to form 4 covalent bonds.

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o To have four singly occupied orbitals for forming 4 covalent bonds, an electron must first be promoted
from the 2s orbital to the empty 2p orbital.
4.1. sp3 hybridisation
Example: Formation of methane molecule, CH4
Four hydrogen atoms have four sets of 1s atomic orbitals

⇀ ⇀ ⇀ ⇀

Before Hybridisation After Hybridisation

Carbon atom: 1s 2s 2px 2py 2pz Carbon atom: 1s sp3 sp3 sp3 sp3
(Ground state)
⇌ ⇌ ⇀ ⇀ ⇌ ⇀ ⇀ ⇀ ⇀

Excitation
Carbon* atom: 1s 2s 2px 2py 2pz

⇌ ⇀ ⇀ ⇀ ⇀

C atom uses one s atomic orbital and three p atomic orbitals to form 4 equivalent sp3 hybrid
orbitals (sp3 hybridisation). These four sp3 hybrid orbitals are arranged in a tetrahedral arrangement.

The four sp3 hybrid orbitals of C overlap in a head-on manner with four 1s atomic orbitals of H atoms,
forming 4 σ bonds, arranged with 109.5° bond angle.
Final molecular orbital:

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4.2. sp2 hybridisation

Example: Formation of ethene molecule, C2H4
Four hydrogen atoms have four sets of 1s atomic orbitals

⇀ ⇀ ⇀ ⇀

Before Hybridisation After Hybridisation

Carbon atom: 1s 2s 2px 2py 2pz Carbon atom: 1s sp2 sp2 sp2 2pz
(Ground state)
⇌ ⇌ ⇀ ⇀ ⇌ ⇀ ⇀ ⇀ ⇀

Excitation
Carbon* atom: 1s 2s 2px 2py 2pz

⇌ ⇀ ⇀ ⇀ ⇀

As each C atom only bonds with three other atoms, the C atoms hybridise only three of the orbitals -
one 2s atomic orbital and two of the 2p atomic orbitals, to form 3 equivalent sp2 hybrid orbitals.
One p atomic orbital remains unchanged (unhybridised). The three sp 2 hybridised orbitals are
arranged in a trigonal planar arrangement with 120° bond angle. The remaining unhybridised p
orbital lies perpendicular (90°) to the plane.

One sp+ orbital of each C atoms overlap together in a head-on manner to form a σ bond. The
remaining two sp2 orbitals of each C atom (two carbon atoms, four sp 2 orbitals) overlap with the 1s
atomic orbital of the 4 H atoms in a head-on manner to form 4 σ bonds.

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The two unhybridised p orbitals overlap in a side-on manner to form a π bond.

Final molecular orbital:

4.3. sp hybridisation
Example: Formation of ethyne molecule, C2H2
Two hydrogen atoms have two sets of 1s atomic orbitals

⇀ ⇀

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Before Hybridisation After Hybridisation

Carbon atom: 1s 2s 2px 2py 2pz Carbon atom: 1s sp sp 2py 2pz
(Ground state)
⇌ ⇌ ⇀ ⇀ ⇌ ⇀ ⇀ ⇀ ⇀

Excitation
Carbon* atom: 1s 2s 2px 2py 2pz

⇌ ⇀ ⇀ ⇀ ⇀

Each C atom uses one s atomic orbital and one p atomic orbital to form 2 equivalent sp hybrid
orbitals. These two sp hybrid orbitals are arranged in a linear arrangement with 180° angle to
minimize repulsion.

One sp hybrid of the C atom overlaps in a head-on manner with the sp hybrid orbital of another C atom
forming a σ bond. The other sp hybrid orbital of a C atom overlap with one 1s atomic orbital of a H atom
forming a σ bond.

Two unhybridised p atomic orbitals of a C atom overlap in a side-on manner with the two unhybridised p
atomic orbitals of the other C atom to form two π bonds.

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Final molecular orbital:

4.4. Differences in C-C bond length

C-C bond length: sp-sp < sp2-sp2 < sp3-sp3
(shortest) (longest)
The increasing p character in the hybrid orbitals results in different size of the hybrid orbitals.

As a result, a C-C bond formed by sp-sp overlap is shorter than that formed by sp 2-sp2 overlap, which in
turn is shorter than that by sp3-sp3.

4.5. Effect of Hybridisation on Bond Length and Bond Strength

The s orbital is spherical and electrons are closer to nucleus.
s-character in hybrid orbitals:
sp3 (25% s character) < sp2 (33% s character) < sp (50% s character)

Thus, the higher the s-character of hybrid orbital,

- The less diffuse the hybrid orbital.
- The more tightly the shared electrons are held by the nuclei.

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- The more effective its overlap with the orbital of the other atom.
- The stronger the bond and the shorter its bond length.
Thus, moving from ethane to ethene to ethyne.
- C-H bond strength increases
- C-H bond length decreases from ethane to ethene to ethyne as shown in the table below:
Compound Ethane, C2H6 Ethene, C2H4 Ethyne, C2H2

Structural Formula

sp3 sp2 sp
Hybrid orbitals
(25% s character) (33% s character) (50% s character)
Orbitals involved in sp3-hybrid orbital of C sp2-hybrid orbital of C sp-hybrid orbital of C with
forming C-H bond with s-orbital of H with s-orbital of H s-orbital of H
C-H bond energy/ kJ mol-
1
410 451 536

C-H bond length/pm 112 110 106

Exercise [NJC/PRELIM 2010/P1/Q3]

Which of the following statements about the orbitals is true?
A. Electrons in a sp2 orbital are held more closely towards the nucleus than electrons in a sp3
orbital.
B. The length of the C-C bond formed by sp2-sp2 overlap is longer than that formed by sp3-sp3
overlap.
C. The shape and size of s-orbitals remain the same as the principal quantum number increases.
D. The energy level of the orbitals of the same principal quantum shell is of the order: s >p > sp3.
Answer: A

Think: What is the type of hybridisation in molecules with lone pair(s) of electrons?
Example 1: Formation of water, H2O
Two hydrogen atoms have two sets of 1s atomic orbitals

⇀ ⇀

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Before Hybridisation After Hybridisation

Oxygen atom: 1s 2s 2px 2py 2pz Carbon atom: 1s sp3 sp3 sp3 sp3
(Ground state)
⇌ ⇌ ⇌ ⇀ ⇀ ⇌ ⇌ ⇌ ⇀ ⇀

Excitation
Oxygen* atom: 1s 2s 2px 2py 2pz

⇌ ⇌ ⇌ ⇀ ⇀

O atom uses one s atomic orbital and three p atomic orbitals to form 4 equivalent sp3 hybrid
orbitals (sp3 hybridisation). These four sp3 hybrid orbitals are arranged in a tetrahedral arrangement.

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Example 2: Formation of ammonia, NH3

Three hydrogen atoms have three sets of 1s atomic orbitals

⇀ ⇀ ⇀

Before Hybridisation After Hybridisation

Nitrogen atom: 1s 2s 2px 2py 2pz Carbon atom: 1s sp3 sp3 sp3 sp3
(Ground state)
⇌ ⇌ ⇀ ⇀ ⇀ ⇌ ⇌ ⇀ ⇀ ⇀

Excitation
Oxygen* atom: 1s 2s 2px 2py 2pz

⇌ ⇌ ⇀ ⇀ ⇀

N atom uses one s atomic orbital and three p atomic orbitals to form 4 equivalent sp3 hybrid
orbitals (sp3 hybridisation). These four sp3 hybrid orbitals are arranged in a tetrahedral arrangement.

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Exercise
Determine the (a) number of sigma and pi bonds and (b) type of hybridization in the following
molecules
i. C in CO2
ii. B in BF3
iii. Si in SiH4
Solution
CO2 BF3 SiH4

(a) 2 sigma and 2 pi bonds (a) 3 sigma bonds (a) 4 sigma bonds
(b) sp (b) sp2 (b) sp3

5. Dative Bonds
a. In some molecules and ions, a covalent bond is formed by one atom donating both electrons for
sharing with another atom.
b. This type of bonding is called coordinate or dative covalent bond.
c. Condition: The acceptor atom must have an empty, low-lying orbital to accommodate the lone
pair electrons from the donor atom
d. It is represented by an arrow ‘→’ from the donor atom to the acceptor atom.
Examples:
Diagram Explanation
BF3:NH3 adduct In BF3, boron has six electrons around it
and is electron deficient.
Nitrogen in NH3 has a lone pair of
electrons which it donates to boron.

Al2Cl6 dimer In AlCl3, Aluminium has six electrons

around it and is electron deficient.
Chlorine in AlCl3 has a lone pair of
electrons which it donates to aluminium.

6. Exceptions to Octet Rule

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a. Molecules with an odd number of electrons (unpaired electrons), e.g. NO, NO2, ClO2
NO NO2 ClO2

b. Molecules with fewer than 8 valence electrons e.g. BF3, AlCl3, BeCl2
BF3 AlCl3 BeCl2

c. Molecules with more than 8 valence electrons (expansion of octet configuration)

This is only possible for elements in Period 3 and after where they have energetically accessible
d-orbitals to accommodate more than 8 electrons i.e. they can expand their octet
structure.
SF6 PF5 XeF4

Why does SF6 exist but not OF6? [OF2 exist. Similarly, PCl5 exist, but not NCl5]
Both O and S belong to Group VI, but in different Periods of the Periodic Table.
O is a Period 2 element.
Oxygen atom: 1s 2s 2px 2py 2pz

(Ground state) ⇌ ⇌ ⇌ ⇀ ⇀
O has only 2s and 2p orbitals. The electrons from the 2nd quantum shell cannot be promoted to the 3rd
quantum shell as it requires too much energy.

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There are 6 valence-shell electrons in the outer shell whose maximum is 8. So oxygen forms two
bonds only i.e. oxygen cannot expand its octet structure. So OF6 does not exist.

S is a Period 3 element.
Sulphur atom: 1s 2s 2px 2py 2pz 3s 3px 3py 3pz

(Ground state) ⇌ ⇌ ⇌ ⇌ ⇌ ⇌ ⇌ ⇀ ⇀
Sulphur atom: 1s 2s 2px 2py 2pz 3s 3px 3py 3pz 3d

(Excited state) ⇌ ⇌ ⇌ ⇌ ⇌ ⇌ ⇀ ⇀ ⇀ ⇀ ⇀
S has 3s, 3p and 3d orbitals. S* can gain sufficient energy to promote the paired electrons to occupy two
vacant 3d orbitals.
It has 6 valence-shell electrons in the outer shell whose maximum is 18.
So S can use its energetically accessible 3d orbitals to expand its octet structure, to form SF 6.

7. Molecular Ions
For positively charged species, electrons are For negatively charged species, electrons are
removed from the less electronegative atoms. added to the more electronegative atoms.
Example: NH4+ Example: NO3−

FIND PICTURE OR SKETCH OUT

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8. Shapes of Molecules and Molecular Ions

a. The arrangement of atoms in space determines the shapes of molecules and molecular ions and is
governed by the Valence Shell Electron Pair Repulsion (VSEPR) Theory
b. There are two types of electron pairs around the atom.
i. Bonding pair electrons
ii. Non-bonding pair electrons or lone pair electrons
Example:

c. 3 Basic principles:
i. Electron pairs repel each other and arrange themselves as far apart as possible to minimize
electrostatic repulsion.
ii. Orbitals containing lone pairs are larger than those containing bond pairs. They take up
more space around the central atom and are, on average, closer to the nucleus.
Hence, they have a greater repulsive effect than the bond pairs.
The order of the extent of repulsion is:
lone pair-lone pair repulsion > lone pair-bond pair repulsion > bond pair-bond pair
repulsion
iii. Repulsion between electron pairs is increased by increase in electronegativity of the central
atom.
d. Steps in predicting shapes:
i. Draw the dot-and-cross diagrams and determine the number of electron pairs (sigma and
pi bonds between two atoms are treated as a single electron pair)
ii. Determine the number of (sigma) bond pairs and lone pairs of electrons around the
central atom.
iii. Find the best geometrical arrangement to maintain the maximum separation of electron pairs
iv. Follow the assignment of shapes according to the VSPER theory.

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8.1. Shapes of Neutral Species

i. Molecules with only two atoms are always linear.
NO

No. of sigma bond pairs 1

(around central atom) (a multiple bond has 1 sigma bond only)
No. of lone pairs NA
Shape of molecule Linear
Bond angle 180°

ii. Two electron pairs

N2O

No. of sigma bond pairs 2

(around central atom)
No. of lone pairs 0
Shape of molecule Linear
Bond angle 180°

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iii. Three electron pairs

BF3 NO2

No. of sigma bond pairs 3 2

(around central atom)
No. of lone pairs 0 1
Shape of molecule Trigonal Planar Bent
Bond angle 120° <120°

iv. Four electron pairs

CH4 SOCl2 H2O

No. of sigma bond pairs 4 3 2

(around central atom)
No. of lone pairs 0 1 2
Shape of molecule Tetrahedral Trigonal Pyramidal Bent
Bond angle 109.5° 107° 105°

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v. Five electron pairs

PCl5 SF4 ClF3

No. of sigma bond pairs 5 4 3

(around central atom)
No. of lone pairs 0 1 2
Shape of molecule Trigonal Bypyramidal See-Saw T-shaped
Bond angle 90° and 120° 90° and 120° 90°

vi. Six electron pairs

SF6 BrF5 XeF4

No. of sigma bond pairs 6 5 4

(around central atom)
No. of lone pairs 0 1 2
Shape of molecule Octahedral Square Pyramidal Square Planar
Bond angle 90° 90° 90°

8.2. Shapes of Charged Species

NO3- SO42- NH4+

No. of sigma bond pairs 3 4 4

(around central atom)
No. of lone pairs 0 0 0
Shape of molecule Trigonal Planar Tetrahedral Tetrahedral
Bond angle 120° 109.5° 109.5°
BrF4+ I2Cl- ICl4-

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No. of sigma bond pairs 4 2 4

(around central atom)
No. of lone pairs 1 3 2
Shape of molecule See-saw Linear Square Planar
Bond angle 120° 180° 90°

8.3. Summary Table of Shapes

No of Electron arrangement No. of Shape Bond Examples
electron sigma Angle
pairs bond
pair +
lone pair
1 Linear 1+0 Linear 180° CO, NO

2 Linear 2+0 Linear 180° BeCl2, CO2,

HCN

3 Trigonal Planar 3+0 Trigonal Planar 120° BF3, SO3,

CO32-

2+1 Bent / V-shaped <120° SnCl2, SO2,

NO2-

4 Tetrahedral 4+0 Tetrahedral 109.5° CH4, NH4+

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3+1 Trigonal pyramidal 107° NH3, SO32-

2+2 Bent / V-shaped 105° H2O, NH2-

5 Trigonal bipyramidal 5+0 Trigonal bipyramidal 90°, PCl5

120°

4+1 See-saw / Irregular 90°, SF4

tetrahedral 120°

3+2 T-shaped 90° ClF3

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2+3 Linear 180° XeF2, I3-,

ICl2-

6 Octahedral 6+0 Octahedral 90° SF6

5+1 Square pyramidal 90° BrF5, IF5

4+2 Square planar 90° XeF4, ICl4-

9. Electronegativity of Central and Bonded Atoms

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i. Central atoms that are more electronegative than the atoms attached will tend to draw the
electron density towards itself. Hence, the bond pairs are closer to the central atom’s nucleus,
resulting in a greater repulsion and larger bond angle
Example: H2O and H2S
H2O H2S

In H2O, oxygen has a greater electronegativity as the central atom than sulfur in H 2S. Hence,
the bond pair electrons are more strongly attracted to oxygen, resulting in greater repulsion
between the bond pairs in water. Hence, the H-S-H bond angle in H2S is less than 105°.

ii. When the bonded atoms are more electronegative than the central atom, they tend to draw
the electron density towards themselves. Hence, the bond pairs are further away from the
central atom’s nucleus, resulting in a lesser repulsion and smaller bond angle.
Example: NH3 and NF3
NH3 NF3

In NF3, fluorine has a higher electronegativity than hydrogen in NH3. Hence, the bond pair
electrons are more strongly attracted towards fluorine in NF 3, resulting in less repulsion
between the bond pairs and thus a smaller F-N-F bond angle.

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10. Covalent Bond Strength

a. Bond length and bond energy measure the strength of a covalent bond. Generally, the longer the
bond length, the lower the amount of energy required to break the bond.
b. Bond length is the distance between the nuclei of the two atoms joined by a covalent bond.
c. A molecule with strong covalent bonds generally has less tendency to undergo chemical change
than does one with weak bonds.
d. Example: H – H bond length in H2.

e. Bond energy is the energy required to break 1 mole of a covalent bond between 2 atoms in the
gaseous state.
Example: A – B (g)  A(g) + B(g) Bond Energy = + x kJ mol-1
f. Factors affecting Bond strength
a. Effectiveness of the overlap
Smaller atoms can approach each other closely
i. shorter bond length
ii. more effective overlap of atomic orbitals
iii. stronger bonds
Example:
Cl – Cl Br – Br I–I
Bond length / nm 0.199 0.28 0.266 ↑
Bond Energy / kJ mol-1 244 193 151 ↓

b. Number of bonding electrons:

Multiple bonds are stronger than single bonds.
For the same bonding atoms, an increase in the number of bonds increases the number of
shared electrons between the atoms i.e. there is increased electrostatic attraction between
the bond-pairs and the two nuclei, hence bond strength is increased.
Example:
C–C C=C C≡C
Bond length / nm 0.154 0.133 0.120 ↓
Bond Energy / kJ mol-1 346 610 837 ↑

c. Bond polarity
- The electronegativity of an element measures the relative tendency of its atom to attract
the shared electron-pair in a covalent bond.

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- A polar covalent bond results if the bonded atoms have different electronegativities. Partial
charges ( + and  -) arise on the two bonded atoms.
- In addition to the existing covalent bond, there is now an increase in electrostatic attraction due
to the two partial charges, which leads to increased bond strength.
- The greater the electronegativity difference between the bonding atoms, the more polar is
the covalent bond, the stronger the bond.
- Based on Pauling’s definition, Fluorine, the most electronegative element, is given an arbitrary
value of 4.0 and all values of the other elements are relative to it. The higher the value, the
stronger the attraction.
Example:
N–H O–H F–H
Electronegativity Difference 0.9 1.4 1.9 ↑
Bond Energy / kJ mol-1 388 463 562 ↑

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Exercise:
Why is the H – Cl bond length shorter and the bond strength stronger than expected?

Bond Bond length / nm Bond Energy / kJ mol-1

H H 0.074 430
Cl Cl 0.198 238
Expected H Cl 0.074+0.198 430+238
= 0.136 = 334
2 2
Actual H Cl 0.128 430

In HCl, Cl, being more electronegative than H, is able to attract electrons more effectively and has a -
charge while H has a + charge. This separation of charge forms a dipole and the bond is polar. The
oppositely charged ends attract each other, causing H and Cl to be closer than expected. As the HCl
bond length is shorter than expected, there is more effective overlapping of atomic orbitals, resulting in
stronger HCl bond energy than expected.

11. Electronegativity and its relationship to bond type

a. Bonding is rarely entirely ionic or covalent, it is usually some mixture of the two.
a. Ionic character in covalent bond results from unequal sharing of bond electrons.
b. Covalent character (covalency) in ionic bond results from polarisation of anions by
cations

b. Polar Bonds
a. When two different atoms of different electronegativity are covalently bonded, the more
electronegative atom pulls the electrons of the covalent bond towards itself and acquires a
small negative charge ( -) while the other atom acquires a small positive charge ( +).
This results in charge separation (dipole) and the bond is polar.
b. The polarity of a bond is measured by dipole moment, μ (usually represented by an arrow
pointing towards the more electronegative atom).
Example:
CO CHCl3 H2O

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c. Dipole moments are like vectors. If two dipoles have the same magnitude and are opposite
in directions, they cancel each other. Hence, the molecule has a zero overall dipole moment
and is non-polar.
Example:
BF3 Trans-C2H2Cl2 SF6

c. Ionic Character in Covalent Bond

a. A molecule is polar only if it has dipole(s) where the distribution of charge in the molecule is
non- symmetrical (i.e. the individual dipoles do not cancel each other).
Hence a polar molecule has an overall dipole moment.
b. Thus, the bonding electrons will not be evenly shared, giving rise to a permanent dipole in
the molecule.
c. Due to the separation of charges, the molecule exhibits some ionic character.
Examples
ICl CH3Cl Cis-C2H2Cl2

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12. Physical Properties of Simple Molecules

a. Simple covalent molecules are attracted to each other by weak van der Waals forces or hydrogen
bonds to form its molecular structure.
b. The molecular structure and type of bonding give rise to the following physical properties.
a. Melting point and boiling point
b. Solubility
c. Electrical Conductivity
12.1. Intermolecular forces
a. During melting and boiling of a simple molecular compound, the intermolecular forces are
overcome.
b. The type of intermolecular forces present within the simple molecules are:
i. Induced dipole- induced dipole interactions (id-id)
ii. Permanent dipole- permanent dipole interactions (pd-pd)
iii. Hydrogen bonding (an extreme form of pd-pd)
c. Comparison in strength of the forces:
Id-id interactions < Pd-pd interactions < Hydrogen Bonding

12.1.1. Induced dipole – Induced dipole interactions (id-id)

i. All molecules exhibit id-id interactions, but it is the only interaction between non-polar molecules.
ii. In a non-polar molecule, like Cl2 or Br2, there is no difference in the electronegativity of the two
bonding atoms and electrons are evenly distributed.
iii. As electrons are constantly moving, there could be an instantaneous dipole formed when there are
more electrons on one side of the molecule. Hence there could be a small partial charge of + on
one atom and - on another atom. This occurs even for a monoatomic element such as Ne.
iv. When another neutral neighbouring molecule approaches, the instantaneous dipole can induce a
temporary dipole in this neighbouring molecule by attracting/repelling its electrons.
v. These temporary weak intermolecular forces of attraction between the two molecules with opposite
partial charges are called induced dipole-induced dipole interactions.

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vi. The diagram shows how a whole lattice of molecules could be held together in a solid by id-id
interactions.
vii. Factors affecting strength of induced dipole – induced dipole attraction
i. Number of electrons / electron cloud size
Molecules which have more electrons can be more easily polarised, resulting in greater
ease of formation of id-id interactions.
The strength of instantaneous dipole – instantaneous dipole interactions increases
with the number of electrons in a molecule.
Example: Comparison of id-id interactions across period 3

No. of
Element Boiling point / °C
electrons
Phosphorus, P4 60 277
Sulfur, S8 128 445
Chlorine, Cl2 34 -34
Argon, Ar 18 -186

ii. Surface area

- Id-id interactions are weak and short ranged. Hence, they operate between portions of
molecules that are close to each other only.
- For different molecules with the same number of electrons, id – id interactions are
stronger in molecules with greater surface area for molecular interactions.
- Straight chain molecules have a more open structure and hence greater surface area for
molecular interactions compared to branched chain isomers which are more compact and
spherical. The id-id interactions are hence stronger in straight chain molecules.

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Exercise
1. Explain the difference in the boiling points between butane and 2-methylpropane
Compound Structure Mr Boiling point
Butane 58.0 -0.5°C

2-methylpropane 58.0 -11.7°C

The butane molecules have a larger surface area for molecule interactions than the branched 2-
methylpropane, and butane can form more extensive induced dipole – induced dipole interactions.
Hence more energy is required to overcome the stronger interactions between butane molecules
than 2-methylpropane. Butane has a higher boiling point.

2. Which molecule, SiH4 or CH4, has a higher boiling point? Explain.

SiH4 has a larger number of electrons than CH4 which allows for a greater ease of formation of
induced dipole-induced dipole (id-id) interactions. Hence, SiH 4 has more extensive id-id interactions
than CH4 and more energy is required to overcome the stronger interactions in SiH 4. Hence, SiH4
has a higher boiling point than CH4.

12.1.2. Permanent dipole- permanent dipole interactions (pd-pd)

a. All molecules experience id-id interactions.
b. Polar molecules such as CHCl3, CH3CHO, NCl3 have additional permanent dipole – permanent
dipole interactions between them due to the non-symmetrical distribution of electrons within the
molecule as the atoms have different electronegativity. The more electronegative atom will attract
electrons towards itself and has a partial negative charge, whereas the less electronegative atom
will have a partial positive charge.

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For molecules with a similar number of electrons,

- Those with permanent dipole – permanent dipole interactions tend to have higher boiling
points than molecules with only instantaneous induced dipole – induced dipole interactions.
- The strength of permanent dipole – permanent dipole interactions increases with
increasing dipole moments.

Exercise:
1. Explain the difference in the boiling points between ethane and fluoromethane.
Compound Mr B.p/ °C
CH3CH3 30.0 -88.5
CH3F 34.0 -78.3

Thinking Process:
Compound Type of molecule B.p/ °C id – id pd – pd
CH3CH3 Non-polar -88.5 √
CH3F polar -78.3 √ √

Answer:
Ethane is a non-polar simple covalent compound held by induced dipole-induced dipole (id-id)
interactions.
Fluoromethane is a polar simple covalent compound held by id-id interactions and permanent dipole
–permanent dipole (pd-pd) interactions.
As stronger attractions hold fluoromethane molecules together, more energy is required to overcome
the attractions.
Hence it has a higher boiling point.

2. Explain the difference in the boiling points between trichloromethane, CHCl3, and
tetrachloromethane, CCl4.
Compound Mr B.p/ °C
CHCl3 119.5 61.2

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CCl4 154 76.8

Thinking Process:
Shape of Type of
Compound B.p/ °C id – id pd – pd
Molecule molecule

CHCl3 Polar 61.2 √ √

CCl4 Non-polar 76.8 √

Answer:
CHCl3 is a simple polar molecule with both induced dipole-induced dipole (id-id) interactions and
permanent dipole-permanent dipole (pd-pd) interactions between its molecules.
CCl4, is a non-polar simple molecule with id-id interactions between the molecules. However, CCl4
contains more electrons than CHCl3 and has stronger id-id interactions between the molecules. The
stronger id-id interactions compensate for the absence of pd-pd interactions in CCl4. More energy is
required to overcome the stronger id-id interactions in CCl4 compared to the interactions in CHCl3.
Hence, CHCl3 has a lower boiling point.

12.1.3. Hydrogen Bonding

a. Hydrogen bonding is an extreme form of permanent dipole-permanent dipole interactions
b. Hydrogen bond is an electrostatic force of attraction between a hydrogen atom covalently bonded
to a highly electronegative atom (F, O or N) and the lone pair electrons of a highly
electronegative atom (N, O or F)
c. When H atom is covalently bonded to a highly electronegative atom, it becomes almost bare or the
nucleus of the H atom becomes very exposed. The attraction between the + of atom with the lone
pair of electron of a highly electronegative atom (F, O or N) is then particularly strong.

Example:
HF NH3 H2O

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d. The criteria for forming hydrogen bonding is

a. H covalently bonded to F, O or N and
b. lone pair of electrons on F, O or N.
e. There are 2 ways of forming hydrogen bonds between 2 molecules:
a. between the same type of molecules (e.g. between HF molecules, shown above) or between
different types of molecules (e.g. between HF and H2O).
Example:

b. between a molecule (that has a hydrogen atom covalently bonded to F, O or N) and a

hydrogen bond acceptor.
(A hydrogen bond acceptor is a molecule that has no hydrogen atoms, but has lone pair of
electrons on a small atom such as F, O or N)
Example:

Examples of other hydrogen bond acceptors that can hydrogen bond with alcohol:

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f. Larger amount of energy is required to overcome the hydrogen bonding present between
molecules, as compared to id-id and pd-pd attractions.
g. The energies of hydrogen bonds typically range from about 4 to 25 kJ mol -1. They are still weaker
than covalent bonds which easily have bond energies greater than 100 kJ mol-1.
h. Number of hydrogen bonds formed per molecule:
No. of H bonded to No. of lone pairs on
Molecule No. of hydrogen bonds per molecule
F/O/N F/O/N connected to H
HF 1 3 1
NH3 3 1 1
H2O 2 2 2

i. Comparison of Boiling points of HF, H2O and NH3

Compoun
Boiling Point (°C)
d
HF 20.0
H2O 100
NH3 -33.0

a. Electronegativity: F>O>N
b. F, being more electronegative than N, is able to attract electrons from H atom more
effectively. Hence, the nucleus of H atom, which is bonded to F, is more exposed. This
results in a stronger attraction between the H atom and the F atom of the neighbouring
molecule. Hence a larger amount of energy is expected to overcome the forces of attraction
between HF molecules.
 Boiling Point: HF>NH3

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c. The expected boiling point is HF > H2O > NH3. However, the boiling point of H2O is found to
be highest. This can be explained by the fact that there is an average of 2 hydrogen bonds
per H2O molecule due to the presence of 2 lone pairs and 2 bond pairs. In both HF and
NH3, there is only one hydrogen bond per molecule.
Hence, the extent of H-bonding in H2O is stronger.
d. The actual order of boiling point is H2O > HF > NH3.
j. Intramolecular H-bonding
a. Hydrogen bonding not only occurs between molecules, but can also exist within the
molecule

b. Due to the proximity of the substituents, the compound undergoes intramolecular

hydrogen bonding
c. Since the 2 substituents are used for intramolecular hydrogen bonding, they have less
tendency to attract neighbouring molecules by intermolecular hydrogen bonding. The
attraction between molecules is the weaker Van der Waals forces instead.

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d. Hence, due to the presence of intramolecular hydrogen bonding, there is less extensive
intermolecular hydrogen bonding. The boiling point of the compound would be lower than
expected.
Exercise:
1. Why is the boiling point of compound A lower than compound B?

Both compounds are polar simple covalent compounds, capable of hydrogen bonding. The distance
between the two functional groups in B is does not allow for intramolecular hydrogen bonding. Instead,
the molecules are attracted by intermolecular hydrogen bonding. Due to the proximity of the 2
functional groups (OH and COOH) in A, it forms intramolecular hydrogen bonding. Hence, it has less
extensive intermolecular hydrogen bonding. Since boiling involves overcoming intermolecular forces
of attraction, the boiling point of A is lower than B as less energy is required to overcome the less
extensive intermolecular hydrogen bonding.

e. Structure and properties of ice

- Each oxygen atom in water forms 2 covalent bonds with H atoms.

- In ice, hydrogen bonding holds the H2O molecules together in a huge 3-dimensional network.

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- The two lone electron pairs on the same O atom are bonded to the hydrogen atoms of 2
neighbouring molecules by hydrogen bonding.
- Each water molecule is surrounded by 4 neighbouring molecules in a tetrahedral cluster.
- The covalent bond length is 0.099 nm whereas the hydrogen bond length is 0.177nm.
- The longer H-bonds in the tetrahedral arrangement of the water molecules result in a fairly
open structure on ice - a significant amount of empty space. This accounts for why ice has a
lower density than water and hence ice floats on water.
- When ice melts, the h-bonding in the tetrahedral cluster is partially broken and the molecules
become more closely packed, thus the volume decreases and density increases.

Summary Table
Types of Weak van der Waals’ Forces
Intermolecular Force
Induced dipole – Permanent dipole – Hydrogen bonding
induced dipole (id-id) permanent dipole
interactions (pd-pd) interactions
Types of molecules ALL molecules Polar molecules Polar molecules with H
between which the Only attraction between bonded to N, O or F.
intermolecular force is non-polar molecules
present
Examples Ne, H2, CO2, BH3, CH4 CHCl3, CH3CHO, PCl3 H2O, NH3, HF, C2H5OH

12.2. Melting Point and Boiling Point

a. During melting and boiling, the intermolecular forces are overcome.
b. In simple molecules, the presence of weak van der Waals’ forces and intermolecular hydrogen
bonding results in low melting and boiling points.
Example: Iodine
a. Iodine molecules are held together in a solid by id-id interactions
b. These weak forces of attraction between molecules can be easily overcome, resulting in a
relatively low melting point (114°C).
c. Iodine appears as a dark grey crystalline solid which sublimes easily to form a purple
vapour.
12.3. Solubility of Simple Molecules
a. When bonds or interactions are formed, energy is released. When bonds or interactions are broken,
energy is taken in.
b. Solubility of a solute (the simple covalent molecule which is dissolving) in a solvent depends on the
strength of solute-solute, solvent-solvent and solute-solvent interactions:

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The solute is soluble when the solute-solvent interaction is sufficient to overcome the
solute-solute interaction and the solvent-solvent interaction.

The solute is insoluble when solute-solvent interaction is insufficient to overcome the

solute-solute interaction and the solvent-solvent interaction.

a. Simple molecules which are non-polar are usually soluble in non-polar solvents.
b. Both the solute and the solvent are likely to have molecules attracted to each other by van der
Waals’ forces of attraction.
c. The intermolecular attractions within the solute and within solvent are disrupted when they mix
with each other. New solute-solvent interactions are formed.
d. When the solute-solute, solvent-solvent and solute-solvent interactions are all comparable in
strength, the solute is able to dissolve in the solvent. The simple covalent compound is soluble
in the solvent.
e. When the solute-solvent interactions are not able to overcome the solute-solute or solvent-
solvent interactions, the solute is not able to dissolve in the solvent, ie insoluble.

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Example: Iodine
a. For I2 to be soluble in water, the I2 molecules should penetrate between the water
molecules. However, hydrogen bonds between the water molecules are relatively strong.
b. I2 can only form weak induced dipole-induced dipole attraction with water
molecules. Little energy is released during the formation of these weaker bonds and it
is not sufficient to overcome the energy required for breaking the relatively stronger H-
bonding.
f. Polar compounds or compounds capable of forming hydrogen bonding with water (eg NH 3,
glucose and ethanol) have greater solubility in water than those which are non-polar.
Example: Ammonia in water
Ammonia has the ability to form hydrogen bonds with water molecules. When the hydrogen
bonds between water molecules are broken, they can be replaced by hydrogen bonds
between water and ammonia molecules.

12.4. Electrical Conductivity

a. Molecular substances are usually non-conductors of electricity due to the absence of mobile
particles such as ions or electrons (Exception: graphite).
b. The electrons are usually localised in the covalent bonds.
c. However, if the molecule ionises in water, e.g. HCl, AlCl3, NH3, it may conduct electricity.

12.5. Dimerisation of Carboxylic Acids, RCOOH

a. The molar mass of some carboxylic acids in the vapour phase is found to be twice that of its molar
mass calculated from its molecular formula.
b. For example, the molar mass of ethanoic acid, CH3COOH, is 60 g mol-1 but the molar mass of
gaseous ethanoic acid determined experimentally is 120 g mol-1
c. This is because such carboxylic acids exist as dimers in the vapour phase. The dimer is made up
of two carboxylic acids bonded to each other by two hydrogen bonds forming an 8-membered ring
as shown below:

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d. Carboxylic acids also exist as dimers in some non-polar solvents such as hexane.
e. However, in aqueous solution, no dimerisation occurs as the carboxylic acid molecules form
hydrogen bonding with water molecules rather than with other carboxylic acid molecules.

13. Giant Molecular Lattice

A solid with a giant molecular lattice is made up of atoms, usually non-metals, held together in an
extensive network by covalent bonds. Such solids are said to have giant covalent structure and are
macromolecules. Some well-known examples with such structures include diamond, graphite and
quartz (silicon dioxide). Such compounds usually have high melting points and exist as solids.
13.1. Diamond
i. The structure of diamond is a three-dimensional array of carbon atoms.

ii. Each carbon atom is sp3 hybridised and covalently bonded to 4 other carbon atoms forming a
tetrahedral. This tetrahedral arrangement is repeated throughout the entire molecule giving rise to

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interlocking hexagonal units so that the resultant structure is extremely strong and rigid. Diamond is
the hardest natural occurring substance and is used in drill bits and glass cutters.
iii. Diamond does not conduct electricity as it does not possess delocalised electrons.
iv. Diamond’s melting point is 3550°C due to the strong covalent bonds between all the carbon
atoms.
v. Diamond is unable to dissolve in water or any other solvent as a lot of energy is required to
overcome the strong covalent bonds between the carbon atoms. This amount of energy is not
compensated by the solvation energy released if diamond dissolves in water or other solvents.
vi. Silicon has the same structure as diamond and is also hard. However, the covalent bonds between
the silicon atoms are weaker than those between the carbon atoms in diamond. Thus, silicon’s
melting point is lower at 1410°C.
Additional Information (for self-reading)
Quartz (Silicon Dioxide)
i. Quartz is silicon dioxide and has the following structure:

ii. From the diagram, each silicon atom is bonded to 4 oxygen atom while each oxygen atom is
bonded to 2 silicon atoms. The arrangement of silicon atoms in quartz is similar to that of
carbon in diamond. The only difference is that for quartz, there is an oxygen atom between 2
silicon atoms.
iii. Since there are no delocalised electrons and silicon(IV) oxide is made up of atoms,
silicon(IV) oxide is an electrical insulator in all states.
iv. Due to the strong covalent bonds between all silicon and oxygen atoms and the rigid 3-
dimensional structure, quartz is very hard and is insoluble in all solvents.
Exercise:
Why is the covalent bond between silicon weaker than those between carbon in diamond?
Solution:
Silicon is larger than carbon. Hence, the bond length between 2 Si atoms would be longer than that
between 2 C atoms. Hence, the bonding between Si is weaker than between C, requiring less energy to
break. Hence, silicon has a lower boiling point than diamond.
13.2. Graphite

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i. Graphite has a layered structure and is made up of planes of interconnected hexagonal rings of
carbon atoms.

ii. Each carbon atom is sp2 hybridised and forms 3 σ bonds with 3 other carbon atoms. Hence, the
geometry is trigonal planar with bond angles of 120° around each carbon atom.
iii. Each carbon has an unhybridised p-orbital, which contains a single electron, will overlap sideways
with the p-orbitals of its immediate neighbouring carbon atoms. This results in an extended π-
electron cloud above and below the plane containing the carbon atoms.
iv. These π-electrons are delocalised over the entire layer and hence, graphite is an electrical
conductor. However, as the electrons are only delocalized within each layer, graphite can only
conduct electricity in a direct parallel to the layers. Therefore, graphite is an insulator in a direction
perpendicular to the layers as the delocalized electrons cannot jump across layers. Graphite is
thus said to exhibit anisotropy, a term given to substances that exhibit properties that depend upon
the direction in which they are measured.
v. The bonds within each layer are covalent but the attraction between each layer is van der Waals
forces.
vi. Graphite has a high melting point of 3730°C due to the presence of strong covalent bonds within
each layer, which requires a lot of energy to overcome these strong forces of attraction. Due to its
high melting point, graphite is used as crucibles for molten metals and re-entry nose cones of
rockets.
vii. The forces of attraction between each layer, van der Waals, are weak. Hence, it allows each layer
to glide over each other. Thus, graphite is soft and used in pencils and as lubricants.

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14. Ionic or Electrovalent Bonding

14.1. Formation of Ionic Bonds
a. Ionic bonds are the electrostatic forces of attraction between the two oppositely charged
ions.
b. They are usually form between metals (low ionization energies) and non-metals (high electron
affinities).
c. In ionic bonding, electrons are completely transferred from one atom to another to satisfy the octet
rule. Metallic atoms (Group I – III) usually lose 1 to 3 valence electrons to form cations, Xn+. On
the other hand, non-metallic atoms (Group V – VII) usually accept 1 to 3 electrons to form anions,
Xn-.
Metals Non-metals
(a) K → K+ + e- (a) Cl + e- → Cl
[Ar] 4s1 [Ar] [Ne] 3s2 3p5 [Ne] 3s2 3p6 = [Ar]
Where [Ar] is 1s2 2s2 2p6 3s2 3p6 Where [Ne] is 1s2 2s2 2p6
(b) Mg → Mg+2 + 2e- (b) O + 2e- → O2-
[Ne] 3s2 [Ne] [He] 2s2 2p4 [He] 2s2 2p6 = [Ne]
Where [Ne] is 1s2 2s2 2p6 Where [He] is 1s2

d. Group IV elements with 4 valence electrons tend not to participate in ionic bonding since a lot of
energy is required for it to lose or gain 4 electrons in order to obtain a stable octet configuration.
Group 0 elements tend not to accept or lose electrons as they already have stable octet
configuration.
14.2. Dot-and-Cross Diagrams
Exercise:
a. NaCl b. MgBr2

c. CaO d. AlF3

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14.3. Structure
Example: sodium chloride, NaCl

a. Ionic solids have ionic lattice structure, consisting of regular three-dimensional arrangement of
positive and negative ions forming a giant network, hence they exist as a crystal lattice or crystalline
solid.
b. The arrangement of the ions depends on the radii of the cations and anions and the ratio of
cations to anions. The ions are arranged so as to maximize attractive forces between ions of
opposite charge and minimize repulsion between ions of like charges, hence achieving the most
stable arrangement.
c. Magnesium oxide also has the same arrangement as sodium chloride.
d. In both compounds, one cation is surrounded by six anions while one anion is surrounded by six
cations. Hence the coordination number is 6.
[The coordination number for a crystal lattice is defined as the number of ions that surround
another ion of opposite charge.]
e. Ionic bonds are non-directional. An ion attracts an oppositely charged ion in all directions without
a preferred orientation.
14.4. Physical Properties
a. High melting and boiling points
Ionic compounds are held together by strong electrostatic forces of attraction between oppositely
charged ions. Hence, a lot of energy is required to overcome these strong attractions resulting in
ionic compounds having high melting and boiling points.
Many ionic compounds have melting points greater than 500°C and hence are solids at room
temperature.

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b. Soluble in polar solvent but insoluble in non-polar solvent

a. Many ionic compounds are soluble in water and other polar solvents. However, they are
insoluble in organic solvents like hexane.
b. When an ionic compound dissolves, the crystal lattice must be broken down and this
requires a lot of energy. This energy can be offset by a release of energy caused by
solvation (if the solvent is water, this is known as hydration).
c. A polar solvent, like water, has a partially positive end (δ+) at the H atom and a partially
negative end (δ-) at the O atom (ref diagram below).
d. When an ionic compound is placed in water, the water molecules can penetrate the crystal
lattice and interact with the ions via ion-dipole interaction (the cations are surrounded by the
(δ-) oxygen end of the water molecule while the anion is surrounded by the (δ+) hydrogen
end of the water molecule).
e. This ion-dipole interaction may release sufficient energy (hydration energy) to overcome the
strong ionic bonds. The salt will hence dissolve and the hydrated ions are free to move
about.

f. However, not all ionic compounds are soluble in water. This happens when the ionic bonds
in the lattice is so strong that the hydration energy is insufficient to overcome them (e.g.
MgO, PbCl2).
g. Ionic compounds are not soluble in non-polar solvents as the ion-solvent interactions are
too weak, releasing too little energy to overcome the strong electrostatic attractions between
the ions in the crystal lattice.
c. Conducts electricity in molten or aqueous state but not in solid state
a. Ionic compounds conduct electricity in the molten or aqueous state as the ions are free to
move. Hence, ionic compounds are good conductors of electricity in the molten or aqueous
state.

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b. However, in the solid state, the ions are held at fixed position and thus unable to act as
mobile charge carriers. Hence, ionic compounds do not conduct electricity when in the solid
state.
d. Hard and brittle
a. Ionic compounds are hard due to the strong ionic bonds between the oppositely charged
ions. Hence ionic compounds are difficult to cut.
b. However, a sharp hard blow will result in a slight displacement along a cleavage plane and
bring ions of like charges together. This will then result in strong repulsion between planes
and cause the ionic crystal lattice to shatter. Thus, ionic compounds are brittle.

e. Ionic Bond Strength

a. Ionic bonds are generally strong forces of attraction and a lot of energy is required to break
such bonds.
b. The strength of an ionic bond is indicated by its lattice energy. Lattice energy is defined as
“the energy released when one mole of an ionic crystalline solid is formed from its
constituent gaseous ions.”
For example, lattice energy of NaCl is equal to the heat released for the reaction
represented by the equation: Na+(g) + Cl-(g) → NaCl(s)
Note:
o Attraction between unlike charges results in stabilisation and energy is given out.
o The greater the attraction, the greater will be the amount of energy given out.
o Conversely, repulsion between like charges results in destabilisation and energy is taken
in.
c. The lattice energy is related to the charges and radii of the cations and anions as shown by
the following expression:
q+ × q -
|Lattice Energy|∝ | |
r+ × r-
Where
q+= charge on cation
q-= charge on anion
r+= radius of cation
r-= radius of anion
(r++r-)= charge on cation

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d. In general, the greater the magnitude of the lattice energy, the stronger the ionic bond.

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e. Variation of lattice energy with charge and size of ions is shown in the table below:

Lattice
Cation charge, Anion charge, Cation size, Anion size,
Compound Energy/ kJ
q+ q- r+/nm r-/nm
mol-1

LiCl +1 -1 0.060 0.181 846

NaCl +1 -1 0.095 0.181 771
MgCl2 +2 -1 0.065 0.181 2493
MgO +2 -2 0.065 0.140 3889

f. Qualitatively, strength of an ionic bond is favoured by

i. Higher charge (greater electrostatic attraction)
ii. Smaller radius/size (shorter interionic distance between ions results in greater
attraction).
14.5. Covalency in Ionic Bond
a. Bonding in ionic compounds is sometimes not entirely ionic. It is sometimes mixed with covalent
character. This is known as covalency in ionic bonds.

Pure Ionic Bond

Ionic Bond with Covalent Character

Covalent

b. Covalency in ionic bonds results from polarisation of the anions by the cations.
c. Polarisation
a. Electron clouds of anions are distorted or polarised by cations when the cations attract the
electrons from the anions towards itself.
b. The electron density of the anion is drawn between the nuclei of the cation and the anion.
Hence, there is partial sharing of electrons. The ionic bond acquires a covalent character.
c. Fajan’s rule: An ionic bond shows the greatest covalent character when:
i. Cation has high charge density - small and highly charged;

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ii. Anion is large.

d. Explanation of the Fajan’s rule:
i. Size & Charge of cation: the smaller the size and greater the charge of the cation,
the higher its charge density and greater the polarising power.
ii. Size of the anion: the larger the size of the anion, the further the outermost
electrons from the nucleus. The electron cloud becomes more easily distorted by
the cation (more polarisable)
Exercise:
1. Explain why LiCl has more covalent character than NaCl.
Solution:
The smaller Li+ has a higher charge density than Na+. Hence it is able to distort the electron
cloud of Cl- anion more, (polarisation) giving rise to more covalent character.

2. Explain why AlCl3 is covalent while AlF3 is ionic.

Solution:
The electron cloud of Cl- anion is larger than that of F- anion. Hence, Cl- anion is more readily
polarised by the high charge density of Al3+cation giving rise to covalent character.
In contrast, the smaller F- anion is not polarised by the high charge density of Al3+ cation, and
hence AlF3 is ionic.

3. The bonding in an ionic compound will show more covalent character if

1. the radius of the cation is large rather than small.
2. the radius of the anion is large rather than small.
3. the charge on the cation is large rather than small
J84
Answer: (C) 2 and 3 only
4. Which of the following sets contain two covalent chlorides and two ionic chlorides?
1. NaCl BaCl2 CCl4 ICl
2. BaCl2 SiCl4 CCl4 SCl2
3. CaCl2 SiCl4 PCl3 SCl2
J91
Answer: (D) 1 only

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15. Metallic Bonding

15.1. Formation of Metallic Bonds
a. Metallic bonding is the electrostatic attraction between the positively charged cations of
the metal and the sea of delocalized or mobile electrons in a metallic lattice structure.
b. Metal atoms have low electronegativities and low ionization energies. Hence, they lose
electrons readily to form positive ions which are arranged in a lattice structure. The valence
electrons lost form a mobile sea of electrons which occupy the space between the metal
cations and are free to move throughout the metal.

15.2. Strength of Metallic Bond

a. Metallic bond is strong and non-directional.
b. The stronger the metallic bond, the higher its melting and boiling point. The strength of
metallic bond is dependent on:
a. Number of electrons contributed to the delocalised sea of electrons. Generally,
the more electrons the metal contribute, the stronger the metallic bond.
Eg: Magnesium, contributing 2 valence electrons, will have stronger metallic bonds
than sodium which only contributes 1 valence electron.
b. Charge of the cation: The higher the charge of the metal cation, the stronger the
electrostatic forces of attraction it has with the valence electrons. Hence, the metallic
bonding will be stronger.
Eg: The cation of magnesium, having a charge of +2, will have stronger metallic
bonds than sodium, whose charge is only +1.
c. Size of the cation: Given the same type of packing, the smaller the size of the
cation, the stronger its charge density. Hence, the attraction with the delocalized
electrons will be greater.
Eg: Given that sodium and potassium are both in group I, sodium, being in period 3
and smaller in size, will have stronger metallic bonding than potassium which is in
period 4.
15.3. Physical Properties
a. High melting and boiling point
Metals are giant lattice structures with strong metallic bonds holding the cations together.
Hence, a lot of energy is required to break these bonds resulting in them having high melting
and boiling points.

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Metal Melting Point/ °C Boiling Point/ °C

Sodium 97.8 890
Magnesium 650 1110
Aluminium 660 2470
Potassium 63.7 774
Iron 1535 3000

b. High electrical conductivity even in the solid state

Metals are good conductors of electricity due to the presence of delocalized or mobile
electrons, functioning as charge carriers that are free to move throughout the 3-
dimensional structure.
Why does electrical conductivity decrease with increasing temperature?
This is because at higher temperature, the positive cations vibrate more causing greater
hindrance to the flow of electrons.

c. Good thermal conductivity

Metals are good conductors of heat. This is due to the fact that when a metal is heated at
one end, the electrons pick up the thermal energy and vibrate faster. They then collide with
the other electrons, passing on the energy to them.
d. Malleable and ductile
Metallic bonds are non-directional. The positively charged ions shield each other’s repulsion
by the sea of delocalized electrons between them and are able to glide over one another
easily without breaking the metallic bond. Therefore, metals can be beaten into shape
(malleable) or drawn into wires (ductile).

Comparison of Bond Types and Properties of Four Different Lattice Structures

Type of Bond Relative strength of bond Bond energy / kJ mol-1
Metallic Bond Strong ≈ 80 to 580
Ionic Bond Strong 120 to 450
Covalent Bond Strong 120 to 550
Hydrogen Bond Fairly weak 13 to 30
Id-id forces Weak 4 to <13

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Summary Table of All Types of Substances

Giant Metallic Giant Ionic Giant Covalent Simple Molecular
Compounds Compounds Compounds Compounds
Simple molecular
Structure Crystalline Lattice Crystalline Lattice Crystalline Lattice
structure
Sodium chloride,
Sodium, Iron, Diamond, graphite, Chlorine, Oxygen,
Examples Iron(III) oxide,
Copper quartz Sulphur dioxide
copper sulfate
Electrostatic
Electrostatic
attraction between
attraction between
the shared
the shared
electron pair and
electron pair and
Electrostatic the nuclei of both
Electrostatic the nuclei of both
attraction between atoms.
attractive between atoms.
Bonding delocalized
oppositely-charged
electrons and Molecules are
ions. Atoms are joined
metal cations. attracted to each
together in a
other by weak van
network through
der Waals forces
strong covalent
of attraction or
bonds
hydrogen bonding.
Physical Properties
Physical state at Solid except for
Mostly liquid/gases
room mercury which is a Solid Solid
Some solids
temperature liquid
High melting and High melting and Low melting and
High melting and
boiling point due to boiling point due to boiling point due to
Melting and boiling point due to
the breaking of the breaking of the breaking of
boiling point the breaking of
strong metallic strong covalent intermolecular
strong ionic bonds
bonds bonds forces of attraction
Hard except for
Hard but malleable
Hardness Hard and brittle graphite which is Soft
and ductile
soft and slippery
Soluble in non-
Soluble in liquid Soluble in polar
polar solvent (e.g
metals. Insoluble solvent (e.g water) Insoluble in all
Solubility water) but
in polar and but insoluble in solvents
insoluble in polar
nonpolar solvents non-polar solvents.
solvents.
Good conductors Non-conductors in
in liquid/molten all states. Some
Electrical Good conductors and aqueous state Non-conductors exceptions are
Conductivity in all states except for graphite those molecules
Non-conductors in which ionizes in
solid state solution.

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16. Resonance (Fundamentals for Organic Chemistry)

- The bonding in some ions and molecules cannot be adequately explained by using one dot-and-
cross diagram or structural formula.
- Example 1: Ozone, O3
- There are two possible structures for O 3, both suggesting that the molecule would be
unsymmetrical, with one oxygen-oxygen bond shorter than the other.

- However, when the oxygen-oxygen bond lengths in O 3 are measured, both are found to be the
same, and mid-way between O-O and O=) bond lengths in other molecules.
Bond Bond length / nm
O-O single bond 0.148
O-O bond in
0.128
ozone
O=O double bond 0.121

- Clearly, both resonance structures are NOT the correct representations of the molecule.
- In reality, the actual structure of the molecule is a hybrid of them, known as the resonance
hybrid.
- In the resonance hybrid, π bonding electrons are delocalised over the oxygen atoms, via the
overlapping of p orbitals of oxygen atoms, which are perpendicular to the plane of the molecule
(containing σ bonds).

- The resonance hybrid is more stable than any of the resonance structures.
- NOTE: “resonance” does not mean the species ‘flip-flops’ back and forth between the 2 canonical
forms. “↔” does not mean the resonance forms are in equilibrium.
- Example2: Nitrate ion, NO3-

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- As shown, the N=O double bond is not rigidly fixed. All the resonance structures have the same
arrangement of nuclei but differ in the arrangement of electrons.
- Experimental evidence again reveals that all the nitrogen-oxygen bonds are identical and
intermediate between an N-O single bond and an N=O double bond.
Bond Bond length / nm
N-O single bond 0.136
N-O bond in NO3- 0.121
N=O double
0.115
bond

- Other species that are resonance stabilised

i. Carbonate, CO32-

ii. Ethanoate, CH3COO-

iii. Benzene, C6H6

The carbon atoms are arranged in the form of a regular hexagon, with all bond angles in the
molecule corresponding to 120°.

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Each of the six carbon atoms in benzene is sp 2 hybridised with an unhybridised p-orbital
perpendicular to the plane.
Benzene has the following bond structural formula:

1. Both structures a and b show that of the six carbon-carbon bonds, three are single bonds
while three are double bonds. The bond length of a C-C single bond is longer than a C=C
double bond. However, experimentally, it is found that all C-C bond lengths in benzene are
equal and this bond length is intermediate between a C-C single bond and C=C double
bond.
2. Sfsfs
3. The two structures a and b are equivalent and they are known as resonance structures
(or canonical forms). Neither of them is an accurate representation but each contributes to
the actual structure. The canonical forms differ only in the arrangement of electrons and
not in the arrangement of atoms. The real molecule is described by an average of the 2
resonance forms:
17. Recycling (Self-Reading)
a. There are only limited supplies of many raw materials. Metal ores such as aluminium ores, coal,
oil and natural gas are a finite resource.
b. The recycling of solid waste is likely to prove of growing importance in future years because it
not only reduces the volume of waster but also yields valuable scrap.
c. Importance of Recycling
a. Conservation of environment
i. Recycling of materials reduce the space needed for waste disposal.

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ii. Recycling also reduces the amount of harmful chemical and greenhouse gases that are emitted
into the environment due to waste disposal at landfills and incineration of waste.
iii. Recycling reduces the demand on raw materials and minerals. Reduced mining and extraction
of raw materials will help to preserve more rainforest and natural habitats. There will be less
habitat destruction and deforestation which will decrease the risk of global warming.
b. Cost and energy saving
i. Products made from recycled materials are cheaper than making products from raw materials.
Much more energy is also used in production of goods from raw materials than from recycling of
materials for production. Hence, recycling of materials helps saves energy and cost of making
products.
c. Sustainable development
i. Recycling now ensures that our future generations will continue to have raw materials and
energy for their future consumption.
d. Materials that are recycled
i. Aluminium
1. Aluminium is the second most extensively used metal in the world today. Some of the uses are
in construction, aircraft manufacturing and also consumer durables like utensils, air-conditioners
and cans.
2. The manufacturing of aluminium is a complex process as it is found in nature as bauxite, a
mixture of aluminium oxides, iron oxides and clay. Producing a can from recycled aluminium
rather than from bauxite saves 95% of the energy. Recycling one kilogram of aluminium saves
20kg of greenhouse gas from the atmosphere.
3. Recycled aluminium can be used in production of aircraft, automobiles, bicycles, boats,
computers, cookware, gutters, siding, wire and cans.
ii. Iron and steel
1. Steel is an alloy of iron, produced by heating coke, iron ore, and limestone in a blast furnace.
2. Steel cans and containers comprise more than 90 percent of the food can market in the United
States, and they contain up to 30% recycled steel. 65% of an average automotive vehicle is
made of steel and iron components, and at least 25% of it are made with recycled steel.
3. Steel is also used as building and construction materials due to its strength and durability.
4. It is more cost-saving to recycle steel than to mine ore for making new steel. Recycling steel
also greatly reduces energy consumption and hence the emission of greenhouse gases during
production.
iii. Plastics
1. Plastics are polymers which are chains of molecules. Plastics are usually made of carbon,
hydrogen, oxygen, and/or silicon. To create polymers, petroleum and other products are heated
and broken down into smaller units called monomers.

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Combinations of monomers produce a variety of plastics of different characteristics.

2. Some of the various plastics are listed in the table below:
Types of Plastics
HDPE High-density polyethylene (i.e., milk jugs)
LDPE Low-density polyethylene
LLDPE Linear low-density polyethylene
PET Polyethylene terephthalate (i.e., soda bottles)
PP Polypropylene (i.e., long underwear)
PS Polystyrene (i.e., packaging "peanuts")
PVC Polyvinyl chloride (i.e., pipes)

3. During recycling the mixture of plastics are sorted by type and sent to a reclaimer. At the
reclaiming facility, the dirt and trash are first removed from the plastic and then cleaned and
grounded into smaller flakes. Flakes are then dried, melted, filtered, and formed into pellets.
New plastic products will be made from the pellets in the manufacturing plants.
4. Recycled plastics can be used as fiber for carpet and textiles or to manufacture bottles.
iv. Paper
1. Fiber is needed to make paper and today, the two main sources are wood and recycled paper
products.
2. Recycled paper processing mills use paper as their feedstock. In a large vessel, the pulper, the
recovered paper is combined in water and blended to separate the fibers in the paper sheets.
Contaminants such as ink, clay and dirt are removed from the slurry by passing through screens
and other separation processes.
3. Recovered fiber can be used to produce new paper products made of 100% recovered fiber or
mixed with new fiber. However, fiber can only be recycled five to seven times before it becomes
unusable in new paper products.
v. Glass
1. Glass, used for the food and beverage industries can be recycled continuously.
2. Most of the recycled glass is used to make new containers. The other uses include kitchen tiles,
counter tops, and wall insulation..
3. Today, recycled crushed glass, known as "cullet," to supplement raw materials to make glass.
Manufacturers mix sand, soda ash, limestone, and cullet together and heat the mixture to a high
temperature and mold it into the desired shape.
4. In this way, money for production is saved as cullet is cheaper than the raw materials and
demands less energy. It also lengthens the furnace life as it requires a lower temperature for
melting.

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