B17CA Student Guide v3

B17CA
Principles of Chemistry
Heriot-Watt University
Edinburgh EH14 4AS, United Kingdom
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©HERIOT-WATT UNIVERSITY B17CA May 2016 v3

Acknowledgements
Thanks are due to the members of Heriot-W att, School of Engineering and Physical Science who
planned and generated this material. Thanks are also due to the members of Heriot-Watt’s SCHOLAR
team in preparing the printed form.
We would like to acknowledge the assistance and contributions from colleagues across the University
and students in preparing this and support material.
©HERIOT-WATT UNIVERSITY B17CA June 2015 v2

Contents
1 PRINCIPLES OF CHEMISTRY ........................................................................................ 2
1.1. INTRODUCTION .......................................................................................................................... 2
1.1.1. Chemistry: a major contributor to the global economy ......................................... 2
1.1.2. Atomic Structure .................................................................................................. 2
1.1.3. The Periodic Table of the Elements ..................................................................... 4
1.1.4. Ions: cations and anions ...................................................................................... 7
1.1.5. Chemical Bonding ............................................................................................... 8
1.1.6. Lewis Structure ................................................................................................... 8
1.2. STOICHIOMETRY ...................................................................................................................... 11
1.2.1. Law of Mass Conservation ................................................................................ 11
1.2.2. Avogadro number NA ......................................................................................... 14
1.2.3. Empirical Formula and Elemental Composition .................................................. 15
1.2.4. Molecular Formula and Molecular weight ........................................................... 16
1.2.5. Using the Chemical Equation ............................................................................ 16
1.2.6. Chemistry in Solution ......................................................................................... 19
1.2.7. Types of Chemical reaction in Aqueous Solution ............................................... 20
2 ATOMIC STRUCTURES AND ORBITALS .................................................................... 28

2.1. INTRODUCTION .......................................................................................................... 28
2.1.1. The Rutherford experiment ................................................................................ 28
2.1.2. Isotopes ............................................................................................................ 29
2.2. THE BEGINNING OF QUANTUM THEORY ........................................................................ 30
2.2.1. Wave-particle duality of light .............................................................................. 30
2.2.2. Atomic spectroscopy ......................................................................................... 33
2.2.3. The atomic theory of Niels Bohr (1885-1962) ..................................................... 34
2.2.4. The limitations of the Bohr model ...................................................................... 35
2.3. QUANTUM (W AVE) MECHANICS ................................................................................... 36
2.3.1. Heisenberg’s uncertainty principle ..................................................................... 36
2.3.2. Schrödinger’s wave equation ............................................................................. 36
2.3.3. Quantum numbers ............................................................................................. 36
2.3.4. Pauli exclusion principle .................................................................................... 38
2.4 MORE ABOUT ATOMIC ORBITALS .................................................................................. 38
2.4.1. Electronic density .............................................................................................. 39
2.4.2 Depicting Atomic Orbitals ................................................................................... 39
2.4.2. Atomic Orbital Size ............................................................................................ 41

2.4.3. Atomic Orbital Energy ....................................................................................... 42
2.5. THE PERIODIC TABLE ....................................................................................................................... 44
2.5.1. Core and Valence Orbitals and Electrons ........................................................... 45
2.5.2. Periods and Groups ........................................................................................... 45
2.5.3. Periodicity in Atomic Properties .......................................................................... 47
3 MOLECULAR SHAPE AND CHEMICAL BONDING ...................................................... 51

3.1. COVALENT BONDING ....................................................................................................................... 52
3.1.1. The octet rule ..................................................................................................... 53
3.1.2. Valency .............................................................................................................. 53
3.1.3. Co-ordinate covalent bonds ................................................................................ 54
3.1.4. Multiple bonds .................................................................................................... 54
3.1.5. Bond polarity ...................................................................................................... 55
3.2. LEWIS STRUCTURE OF MOLECULES..................................................................................................... 56
3.2.1. Charged and delocalized species ....................................................................... 56
3.2.2. Exceptions to octet rule ...................................................................................... 58
3.2.3. Bridging atoms ................................................................................................... 60
3.2.4. Bond order, bond length and bond energy .......................................................... 61
3.3. MOLECULAR SHAPE......................................................................................................................... 64
3.3.1. Geometry and shape .......................................................................................... 64
3.3.2. VSEPR............................................................................................................... 65
3.3.3. Further examples of Lewis structure / VSEPR .................................................... 71
3.3.4. Inert pair effects ................................................................................................. 73
3.3.5. Shape and Molecular Dipoles ............................................................................. 75
3.4. VALENCE BOND (VB) THEORY ........................................................................................................... 77
3.4.1. Basis .................................................................................................................. 77
3.4.2. Hybrid Orbitals ................................................................................................... 78
3.4.3. VB construction .................................................................................................. 80
3.5. MOLECULAR ORBITAL (MO) THEORY- A BRIEF INTRODUCTION ............................................................... 82
4 CHEMISTRY OF THE ELEMENTS OF THE MAIN GROUP ........................................... 83

4.1. INTRODUCTION............................................................................................................................... 84
4.1.1 Natural abundance .............................................................................................. 84
4.1.2 Classification of Main Group elements................................................................. 85
4.1.3. Physical forms of the Main Group Elements ....................................................... 85
4.1.4. Properties of the Main Group compounds........................................................... 88
4.3 CHEMISTRY OF HYDROGEN H ............................................................................................................. 90
4.3.1. Properties........................................................................................................... 90
4.3.2. Compounds of Hydrogen ................................................................................... 91

4.3.3. Hydrogenation Reactions ................................................................................... 93
4.3.4. Production of Hydrogen ...................................................................................... 94
4.3.5. Industrial uses of Hydrogen ................................................................................ 95
4.3.6. Reactions of Main Group Hydrides ..................................................................... 96
4.3.7 . Hydrogen Bonding ............................................................................................. 97
4.4. CHEMISTRY OF THE HALOGENS (GROUP 17) ........................................................................................ 98
4.4.1. Properties .......................................................................................................... 98
4.4.2. Production of Halogens ...................................................................................... 98
4.4.3. Industrial use of Halogens .................................................................................. 99
4.4.4. Common stoichiometries of the Halides of period 2 and 3 ................................ 100
4.4.5. Hydrogen halides ............................................................................................ 102
4.4.6. Halogen oxyacids ............................................................................................ 102
4.4.7. Interhalogen Fluorides ..................................................................................... 103
4.5. CHEMISTRY OF THE CHALCOGENS (GROUP 16: O, S, SE) ..................................................................... 104
4.5.1. Production ....................................................................................................... 104
4.5.2. Stoichiometry of most common oxides of period 2 and 3 ................................. 104
4.5.3. Reactivity of Alkali metals with O2, H2O, .......................................................... 104
4.5.4. Oxides of group 14 (C, Si) ............................................................................... 105
4.5.5. Oxides of group 15 (N, P, As) .......................................................................... 107
4.5.6. Oxides of Sulfur ............................................................................................... 109
4.6. ENVIRONMENTAL IMPACT OF MAIN GROUP COMPOUNDS .................................................................. 110
4.6.1. Acid rain .......................................................................................................... 110
4.6.2. Ozone depletion .............................................................................................. 111
4.6.3. Greenhouse Effect .......................................................................................... 113
5 ORGANIC CHEMISTRY INTRODUCTION .................................................................. 115

5.1. INTRODUCTION ............................................................................................................................ 116
5.2. ALKANES .................................................................................................................................... 118
5.2.1. Structure and bonding in Alkanes .................................................................... 119
5.2.2. Drawing and writing structure for alkanes ........................................................ 121
5.2.3. Isomerism in Alkanes ...................................................................................... 124
5.2.4. Conformations of Alkanes ................................................................................ 127
5.2.5. Reactions of Alkanes ....................................................................................... 127
5.3. HALOGENOALKANES (ALKYL HALIDES) ............................................................................................. 133
5.3.1. Structure and Reactivity .................................................................................. 133
5.3.2. Substitution Reactions SN2 and SN1 ................................................................ 134
5.3.3. Elimination Reactions of Alkyl Halides E2 and E1 ............................................ 141
5.4. ALKENES ..................................................................................................................................... 145
5.4.1. Structures and Reactivity ................................................................................. 145
5.4.2. Synthesis of Alkenes ....................................................................................... 147
5.4.3. Reactions of Alkenes ....................................................................................... 149

5.5. ALCOHOLS .................................................................................................................................. 152
5.5.1. Structure, Properties, and Acid-Base Reactions .............................................. 152
5.5.2. Synthesis of Alcohols ...................................................................................... 159
5.5.3. Oxidation of Alcohols ....................................................................................... 162
5.5.4 Grignard Reagents ........................................................................................... 165
GLOSSARY ..................................................................................................................... 169

TOPIC 1. PRINCIPLES OF CHEMISTRY 1
Topic 1
Contents
1.1 INTRODUCTION .................................................................................................. 2
1.1.1. Chemistry: a major contributor to the global economy. .............................. 2
1.1.2. Atomic Structure ........................................................................................ 2
1.1.3. The Periodic Table of the Elements ........................................................... 4
1.1.4. Ions: cations and anions. ........................................................................... 7
1.1.5. Chemical Bonding ...................................................................................... 8
1.1.6. Lewis Structure .......................................................................................... 8
1.2. STOICHIOMETRY............................................................................................... 9
1.2.1. Law of Mass Conservation ....................................................................... 10
1.2.2. Avogadro number N A ............................................................................... 12
1.2.3. Empirical Formula and Elemental Composition ....................................... 13
1.2.4. Molecular Formula and Molecular weight ................................................ 14
1.2.5. Using the Chemical Equation. .................................................................. 14
1.2.6. Chemistry in Solution ............................................................................... 18
1.2.7. Types of Chemical reaction in Aqueous Solution ..................................... 20
Prerequisite knowledge
Before you begin this Topic, you should be able to understand the meanings of the following
terms:
atomic structure; electronic configuration; the octet rule; the periodic table of the elements
and the chemical bond (ionic and covalent bond).
Learning objectives
After studying this Topic, you should be able to:
• Calculate in mole and determine the molecular formula of a compound.
• Balance chemical equations - of chemical reactions in aqueous solution, acid base
reactions, redox reactions.
• Determine oxidation numbers.
• Balance redox equations using half reactions in acidic and in basic solutions.

1.1. Introduction
1.1.1. Chemistry: a major contributor to the global economy.

Chemistry is the Science of the composition, structure, properties and reactions of atomic
and molecular systems. Our knowledge of Chemistry is applied by the Chemical Industry to
transform raw materials such as oil, natural gas, air, water, metals and minerals into more
than 70,000 different products. These products are used in four main sectors of activity:
energy, life science, chemical, and electronics. Chemistry is a major contributor to the global
economy.
1.1.2. Atomic Structure

Various models for the structure of atoms have been
proposed. In 1911, Ernest Rutherford theorised that atoms
have their positive charge concentrated in a very small
nucleus and introduced the Rutherford model of the atom: a
small nucleus made of neutron(s) and positively charged
proton(s) placed in an electron cloud made of negatively
charged electron(s).
Ernest Rutherford (1871-

1937) received the Nobel
prize in Chemistry in 1908.
He is considered the father
of nuclear physics.
Figure 1. Rutherford’s model of the atom: a small positively
charged nucleus in a cloud of negatively charged electron(s).
• The nucleus is made of nucleon particles, either protons (positively charged particles)
or neutrons (uncharged particles).
• The electrons in orbits are negatively charged. When the number of electrons equals
the number of protons the atom is electrically neutral.
Note: A cation is an atom with more protons than electrons and so is positively charged. An
anion is an atom with more electrons than protons and so is negatively charged.

The Bohr model of the atom represents the atomic nucleus at

the centre and electrons in orbits around it. Each orbit has a
set energy and electrons have the energy of their orbit.
Electrons can move from one orbit to another by gaining or
losing a discrete amount of energy.
Niels Henrik David Bohr

received the Nobel prize in
Physics in 1922 for his
fundamental contributions
to understanding atomic
structure and quantum
Figure 2. Bohr model of an atom of Hydrogen, showing mechanics.
one electron transiting from level n=3 to n=2 and emitting
a quanta of energy hν.
• An electron shell is an orbit of electrons around the nucleus. The closest shell to the nucleus
is called the first shell, and is followed by the second shell and so on.
• Each shell consists of one or more sub-shells (atomic orbitals) and can contain only a fixed
number of electrons:
1st shell: 2 electrons in atomic orbital 1s
2nd shell: 8 electrons in atomic orbital 2s and 2p
3rd shell: 18 electrons in atomic orbital 3s, 3p and 3d
4th shell: 32 electrons in atomic orbital 4s, 4p, 4d, 4f
The electronic configuration describes the distribution of electrons around the nucleus in
shells and sub-shells.
Example: The electronic configuration of Neon.
n=2
n=1
2 2 6
Neon: 1s 2s 2p

Any atom can be written: X is the Chemical Symbol of the Element.

A A is the mass number (number of nucleons).
Z
X Z is the atomic number (number of protons).
An element X is characterised by a number of protons Z (atomic number). Any element can

have several isotopes.
Isotopes of the same element have the same number of protons Z therefore share the same
chemical symbol X, but have a different number of neutrons (a different mass number A).
Example. The natural isotopes of hydrogen.
1 2 3
1H 1H 1H
protium deuterium tritium
1.1.3. The Periodic Table of the Elements

All the elements are listed in the Periodic Table in horizontal
periods with increasing atomic number Z and organised in
vertical groups according to their chemical properties. Groups
are now numbered from 1 to 18.
Dmitri Ivanovich
Mendeleev (1834-1907)
formulated the periodic
Law of the element and
discovered the periodic law
of the elements.
The elements are organised in groups according to their chemical properties and within
their group, share some similarities in their electronic configuration.

The blocks of elements. The periodic table can be split into blocks corresponding to the
electronic configuration of the outer shell; into s-, p-, d- and f-blocks.
• The s-block is constituted by the elements from group 1 and 2 plus helium.
• The p-block is constituted by the elements from groups 13 to 18.
• The d-block is constituted by elements from groups 3 to 12.
• The f-block is constituted by some elements from period 6 and 7. These elements
are also called the Lanthanides and the Actinides.
Other groupings have been made and are in common usage.
• The Main Group Elements are the s- and p-block elements.

• The Transition Elements are the d-block elements.
• The Lanthanides and Actinides are the f-block elements.
The following groupings are based on the chemical properties and the conductivities of the
elements.
• Alkali Metals (elements of group 1 except hydrogen: include lithium Li, sodium Na
and potassium K).
• Alkaline Earth Metals (elements of group 2: include beryllium Be, magnesium Mg
and calcium Ca.
• Transition Metals (the d-block elements: include scandium Sc, titanium Ti,
vanadium V, chromium Cr, manganese Mn, iron Fe, cobalt Co, nickel Ni, copper Co,
zinc Zn.
• Other Metals (metal elements from the p-block: include aluminium Al, gallium Ga.
• Metalloids (have intermediate properties between metal and non metal, they are in
the p-block: include boron B, silicon Si, germanium Ge, arsenic As
• Non-Metals (include hydrogen H, carbon C, nitrogen N, oxygen O, phosphorus P,
sulfur S, selenium Se.
• Halogens (include fluorine F, chlorine Cl, bromine Br, iodine I).
• Noble Gases (include helium He, neon Ne, argon Ar, krypton Kr.
• Rare Earth Elements (include the lanthanides and actinides).
Periods
The elements of the same period have the same number of electron shells.
• The elements of the first period H and He have their electrons in the first shell.
• The elements of the second period (Li to Ne) have their electrons in the first
and second shell.
• The elements of the third period (Na to Ar) have their electrons in the first,
second, and third shell.
The Valence Shell is the outer-shell of an atom, where valence electrons are found. The
valence electrons are responsible for the chemical properties of the elements.

The Core Shells are fully filled by the core electrons. Core electrons do not generally take
part in chemical reactivity. When writing electron configurations, the core electrons are
replaced with the name of the noble gas in brackets that has the same configuration.
Example: Sulfur, S, Z = 16, electronic configuration: 1s2, 2s2, 2p6, 3s2, 3p4
2 4
32 1s2, 2s2, 2p6, 3s2, 3p4 hence [Ne] 3s 3p
S
16 core shells valence shell
The valence electrons are the electrons of the outer-shell (the valence shell)
Responsible for the chemical properties of the elements.
• Can be removed from the shell
• Can be shared between atoms
• Are available for chemical reactions
Valence electrons and the periodic table of the elements.

Since the elements are organised in the periodic table according to their electronic
configuration, we can find the number of valence electron of an element from its position in
the table.
Valence electrons of the main group elements (s-block and p-block)

s-block elements (same as group number (except He has two valence electron)
e.g. Sodium Na: [Ne] 3s1
Calcium Ca: [Ar] 4s2
p-block elements (Group 13 to 18) (group number -10)

e.g. Gallium Ga: [Ar] 3d10 4s2 4p1
Germanium Ge: [Ar] 3d10 4s2 4p2
Arsenic As: [Ar] 3d10 4s2 4p3
Selenium Se: [Ar] 3d10 4s2 4p4
Bromine Br: [Ar] 3d10 4s2 4p5
Krypton Kr: [Ar] 3d10 4s2 4p6

Valence electrons of the transition metals (d-block; group 3 to 12).

Sc to Zn: the electrons responsible for the properties of the transition metals are found in
the 3d/4s shell. This happens because the two shells 4s and 3d are on very similar energy
levels (see: d electron count).
Scandium Sc: [Ar] 3d1 4s2

Titanum Ti: [Ar] 3d2 4s2
Vanadium V: [Ar] 3d3 4s2
Chromium Cr: [Ar] 3d5 4s1
Manganese Mn: [Ar] 3d5 4s2
Iron Fe: [Ar] 3d6 4s2
Cobalt Co: [Ar] 3d7 4s2
Nickel Ni: [Ar] 3d8 4s2
Copper Cu: [Ar] 3d10 4s1
Zinc Zn: [Ar] 3d10 4s2
Chemical reactions use only the valence electrons.

Valence electrons are available for reactions and bonding, they can be added to or removed
from the valence shell or shared between different atoms to form chemical bonds.
1.1.4. Ions: cations and anions.

Elements tend to acquire or lose electrons in order to achieve the same electron count as
the nearest group 18 element (the noble gases).
The elements of the main group (s-block and p-block) with 1, 2 or 3 valence electrons tends
to form cations by losing all their valence electrons to have the electronic configuration of the
noble gases.
e.g. Sodium Na [Ne] 3s1 loses its valence electron to form Na+ [Ne]
Magnesium Mg [Ne] 3s2 loses its valence electrons to form Mg2+ [Ne]
Aluminium Al [Ne] 3s2 3p1 loses its 3 valence electrons to form Al3+ [Ne]
The elements of the main group (s-block and p-block) with 5, 6 or 7 valence electrons tends
to form anions by gaining extra valence electrons to have to electronic configuration of the
noble gases.
e.g. Nitrogen N, [He] 2s2 2p3 acquires 3 valence electrons to form N3- [Ne]
Oxygen O, [He] 2s2 2p4 acquires 2 valence electrons to form O2- [Ne]
Fluorine F, [He] 2s2 2p5 acquires 1 valence electron to form F- [Ne]
Note about hydrogen

Hydrogen 1s1 can lose an electron to form a proton H+
can also gain an electron to form ion hydride H-
The transition elements tend to lose any electrons of their s-shell plus one, two or more
electrons from their d-shell, forming several cations.

Example, Cu loses one electron from its s-shell to form Cu+, and can also lose an extra
electron from its d-shell to form cu2+.
1.1.5. Chemical Bonding

Ionic bonding
The ionic bond is a chemical bond formed through electrostatic attraction between a cation
and an anion.
Covalent bonding
A covalent bond is formed when two electrons are shared between two atoms, generally
allowing each of them to have the electronic configuration of a noble gas. When the
electrons are not shared equally between the two atoms, one attracting more the electron
density to its own nucleus, the covalent bond is polar, and the bond display a degree of ionic
character.
1.1.6. Lewis Structure

Chemical reactions are the result of bond breaking and bond making, involving the valence
electrons. Lewis structures (also called Lewis dot diagrams), show the distribution of the
valence electrons around the atoms. The Lewis structures give a simple way of following the
formation of ions or molecules from atoms, keeping track of all bonding and lone-pair
electrons.
Table 1. Lewis Structures of the first 18 elements.
Group 1 2 13 14 15 16 17 18
Valence electron 1 2 3 4 5 6 7 8
Valence number 1 2 3 4 3 2 1 0
Period 1 H He
Period 2 Li Be B C N O F Ne
Period 3 Na Mg Al Si P S Cl Ar
• Valence electrons are represented by dots arranged around the element symbol.
• Lone-pairs are represented as double dot.
• A covalent bond is formed when a pair of electron is shared by two atoms, bonding
pairs are represented by a double dot (or more usually a line) between two atoms.
Note. The valence number is the number of bonds that an atom requires to satisfy the octet
rule. The valence number is the number of bonding electrons. Lone-pair electrons are non-
bonding valence electrons and are not included in the valence number.

Lewis Structure of Molecules

Molecule Molecular formula H Lewis dot structure Lewis structure
H H H
C H H H
Ethanol C 2H 6O H H C C O H C C O
C H O H H H
H H H H
20 ve = 8e(C) + 6e(H) +6e(O)
• Keep track of the number of valence electrons.

• Check the valence number of each atom (e.g. 4 for carbon, 1 for hydrogen).
Lewis Structures showing the formation of Chloride ion from Chlorine.
Cl + Cl
chlorine atom electron chloride ion

7 valence electrons 8 valence electrons
• For an anion, add electrons to the valence electrons of the element.

• Check that the anion satisfies the octet rule.
• The Lewis structure of an anion is placed within brackets, with the charge placed in
superscript.
Lewis Structures of polyatomic ions

Ion formula Keep track of valence electrons Lewis dot structure Lewis structure
N C S N C S
NCS- N C S or or
Thiocyanate ion N C S N C S
-
16 ve = 5e(N) + 4e(C) +6e(S)+ 1e
Two Lewis dot structures can be drawn: each has 16 valence electrons;
all atoms satisfy the octet rule- both are valid pictures of the ion.
1.2. Stoichiometry
Historical link:

Antoine de Lavoisier (1743-1794) carefully monitored the mass

of reagents and products during chemical reactions and
discovered the law of conservation of mass.
The law states that in any system closed to all transfers of
matter and energy, the mass of the system remains constant
over time, as system mass cannot change quantity if it is not
added or removed. During any chemical reaction in an isolated
system, the mass of the reactants must equal the mass of the
products.
2 Hg (l) + O 2(g) → 2 HgO (s)
Oxidation reaction of mercury in a closed system lead

Lavoisier to the discovery of Oxygen and to the Law of
Conservation of Mass. This lead the way to quantitative Antoine de Lavoisier
chemistry (stoichiometry). (1743-1794) discovered
the law of conservation of
mass.
1.2.1. Law of Mass Conservation

The law of mass conservation implies that atoms can neither be created nor destroyed
during a chemical reaction, although they may be rearranged, and/or their state of matter
may change.
The direct implication of the law of mass conservation is that chemical reaction equations
must be balanced, as atoms are neither created nor destroyed during a chemical reaction.
The numbers of each atom involved in the reaction must be the same before (as reagents)
and after (as products).
Example of the combustion of ethanol C 2 H 5 OH.
The qualitative equation does not give any stoichiometric information. Ethanol (C 2 H 5 OH)
plus oxygen (O 2 ) give carbon dioxide (CO 2 ) plus water (H 2 O).
C2H5OH + O2 CO2 + H2O
• The number of carbons has to be balanced first:

• Every molecule of ethanol has two carbon atoms and so will form two molecules of
carbon dioxide.
C2H5OH + O2 2 CO2 + H2O
• Then the number of hydrogen atoms has to be balanced:

• Every molecule of ethanol has six hydrogen atoms and three water molecules will
form. As each water molecule has two hydrogen atoms for every molecule of ethanol.
C2H5OH + O2 2 CO2 + 3 H2O

• Finally the number of oxygen atoms has to be balanced:

• The combustion of one molecule of ethanol creates two molecules of carbon dioxide
plus three molecules of water: a total of (2x2) plus (3x1) equal seven oxygen atom.
One of these atoms comes from the molecule of ethanol and the six other atoms
come from three molecules of oxygen.
C2H5OH + 3 O2 2 CO2 + 3 H2O
The equation is now balanced the atoms present on one side of the reaction (two carbon, six
hydrogen and seven hydrogen) are also found on the other side of the reaction.
Hints: Balancing chemical equation without trouble:

• Start with the most associated atoms: here the carbon.
• Work your way looking at the less and less associated atoms.
• Here we finish with oxygen because it is in its O 2 state as reagent, not associated
with any other atom.
Example of the precipitation of barium sulfate from barium chloride and aluminium
sulfate.
BaCl2 (aq) + Al2(SO4)3 (aq) Ba(SO4) (s) + AlCl3 (aq)
• Balance the sulfates
BaCl2 (aq) + Al2(SO4)3 (aq) 3 Ba(SO4) (s) + AlCl3 (aq)
• Balance the barium
3 BaCl2 (aq) + Al2(SO4)3 (aq) 3 Ba(SO4) (s) + AlCl3 (aq)
• Balance the chloride
3 BaCl2 (aq) + Al2(SO4)3 (aq) 3 Ba(SO4) (s) + 2 AlCl3 (aq)
• Check the aluminium: the chemical equation is balanced!
Note on dissolution: When an ionic solid is dissolved in water, the molecules of water
create a shell around the anions and the cations (phenomenon known as solvation). This
leads to the weakening of the ionic bond and the separation of the ions.
Note on nomenclature. Solvated ions can be noted in their separated form (Ba2+ + Cl-) or
as aqueous compound BaCl 2(aq) ,(aq) notation implies that the ions are solvated in water.
BaCl2 (s) BaCl2 (aq) Ba2+(aq) + 2 Cl-(aq)

water

1.2.2. Avogadro number NA

Amedeo Avogadro noticed that the volume of any gas under a
given pressure and temperature condition is proportional to the
number of atoms or molecules regardless of the nature of the
gas.
N A is defined as the number of carbon atoms in 12 grams of

12
C. Note 12 gram of Carbon make one mole.
N A = 6.022 x1023 mol-1
Avogadro’s constant is a scaling factor between macroscopic

(observation scale) and microscopic (atomic scale).
Example:
2 gram of hydrogen gas, H 2 has 6.022 x 1023 molecules of H 2 .
12 gram of 12C carbon has 6.022 x1023 atoms of C.

Amedeo Avogadro (1776-
23
32 gram of dioxygen gas, O 2 , has 6.022 x10 molecules of 1856). Contributed to
O2. molecular theory and
discovered the Avogadro
law. The number of
58.45 gram of NaCl is made of 6.022 x1023 ions of sodium and
elementary entities in one
6.022 x1023 ions chloride.
mole of substance is
named after him.
The mole (mol), a unit of quantity.
One mole is a unit of quantity: it is 6.022 x1023 entities.
Question: Calculate the mass of 6.022 x 1023 atoms of carbon 12.

Mass of a proton m = 1.6726 x10-27 kg
Mass of a neutron m = 1.6749 x10-27 kg
Mass of an electron m = 9.109 x10-31 kg
Answer: One carbon atom has six protons and six neutrons and six electrons.
mass = 6.022 x 1023 x [6(1.6726 x10-27) + 6(1.6749 x10-27) + 6(9.109 x10-31)] kg
mass = 0.012 kg (ie 12.0 g)
Molar mass: M is the mass (in gram) of one mole (mol) of any species. Unit of M: (g.mol-1).
M molar mass in gram per mole (g.mol-1)
m m mass in gram (g)
M = n quantity in number of moles (mol)
n
The molar mass of carbon 12 is M = 12 g.mol-1
Molecular weight: MW, is the mass in gram of one mole of molecule; MW has the same
unit as Molar mass: (g.mol-1)

Note. Always check the coherence of the units and remember to write the units; in an exam
question the unit is as important as the value you had calculated!
1.2.3. Empirical Formula and Elemental Composition

The empirical formula is the simplest positive integer (whole number) ratio of atoms present
in a compound.
Examples.
Hydrogen peroxide whose molecular formula is H 2 O 2 , has the same number of hydrogen
and oxygen atoms: its empirical formula is HO.
Glucose whose molecular formula is C 6 H 12 O 6 , and ribose C 5 H 10 O 5 both have the same
empirical formula: CH 2 O.
Note. The Formula is called empirical because it is measured by experiment. When an

unknown compound is analysed by elemental analysis; it is combusted and the products of
its combustion (e.g. CO 2 , H 2 O, N 2 , SO 2 ) are measured. The result of an elemental analysis
is presented as a percentage (%) by mass of C, H, N and S. A percentage (%) is expressed
in gram per 100 gram.
Exercise. To find the empirical formulae of a compound from its elemental composition.
A solid has 12% carbon, 40% calcium and 48% oxygen. Calculate its empirical formula.
• First, find the number of moles per 100g for each atom: use the formula:
m
n=
M
• Divide the percentage value (g per 100g) by the atomic mass M (g.mol-1) of the
elements.
n c = 12 (g/100g) / 12 (g.mol-1) = 1 mol/100g
n Ca = 40 (g/100g) / 40 (g.mol-1) = 1 mol/100g
n O = 48 (g/100g) / 16 (g.mol-1) = 3 mol/100g
• Find the simplest positive integers: divide all of these values by the smallest.
1 C, 1Ca, 3O the smallest is 1.
The empirical formula is CaCO 3
Note. The atoms in the empirical formula: the hill notation uses C, H then in alphabetical
order followed by their integer.
Exercice. A liquid has the following composition: C, 14.5%; Cl, 85.5%. Find the empirical
formula.

• Find the number of mole per 100g.

n c = 14.5 / 12.01 = 1.207 mol/100g
n Cl = 85.5 / 35.45 = 2.412 mol/100g
• Find the simplest positive integers.

1.207 C, 2.412 Cl:
Simplest positive integer of C : 1.207/1.207 = 1
Simplest positive integer of Cl: 2.412/1.207 = 2
The empirical formula is CCl 2
Empirical formula indicates the ratio of each type of atom in a chemical compound. It does
not give any information on structure.
1.2.4. Molecular Formula and Molecular weight

The Chemical formula indicates the numbers of each type of atom in a chemical compound.
When the compound is a molecule we often use the term: Molecular Formula.
Find the molecular formula from the empirical formula and the molecular weight
Example. The empirical formula (EF) of glucose is CH 2 O.
Glucose has a molecular weight of MW = 180.16 g/mol

(This means that one mole of molecule of glucose weighs 180.16 g)
• Find the multiplying factor to obtain the molecular formula from the empirical formula.
CH 2 O has a molar mass of EFW = 12+2+16 = 30 g mol-1

Multiplying factor = MW/EFW = 180.16 / 30 = 6
The molecule of glucose has six carbon atoms
• To get the right numbers of each atom in one molecule we multiply each atom in the
empirical formula by the multiplying factor six.
6 x (1) C; 6 x (2) H; 6 x (1) O
The molecular formula of Glucose is MF = C 6 H 12 O 6
1.2.5. Using the Chemical Equation.

The chemical equation is used to set up and to monitor chemical reactions.
e.g. Sodium thiosulfate (Na 2 S 2 O 3 ) reacts with chlorine (Cl 2 ) in water (H 2 O) to give sodium
bisulfate (NaHSO 4 ) and hydrogen chloride (HCl).
If we want to use 1.58 g of sodium dithionite in this reaction, calculate the mass of chlorine
the reaction will consume.

• First, balance the chemical equation:
Na2S2O3 + 4 Cl2 + 5 H2O 2 NaHSO4 + 8 HCl
Na 2 2
S 2 2
O 3 5 8
H 10 2 8
Cl 8 8
Every mole of sodium thiosulfate reacts with four moles of chlorine gas.
• Calculate the number of mole of sodium thiosulfate introduced in the reaction.
m m = 1.58 g
n= M = 158.11 g/mol
M
n = 0.01 mol
The number of moles of Chlorine needed is 4 times more = 0.04 mol.
• Calculate the mass of chlorine needed.

Using the formula: m = n x M, where: M Cl2 = 70.91 g/mol;
n = 0.04 mol
m = 2.84 g
Calculate the expected mass of sodium bisulfate (NaHSO 4 ) produced.
• Use the chemical equation to determine the number of mole of NaHSO 4 to be

produced.
0.01 mol of Na 2 S 2 O 3 can produce 0.02 mol of NaHSO 4
• Calculate the mass using the molar mass of NaHSO 4 .

Using the formula: m = n x M where M NaHSO4 = 120.06 g/mol;
n NaHSO4 = 0.02 mol
m = 2.40 g
Reaction yield is the amount of product obtained in a chemical reaction, expressed in gram.
The theoretical yield is the amount of product expected to be formed and is calculated using
the chemical equation. The actual yield is the amount of product physically measured by the
experimentalist.

Percentage yield is used to measure the effectiveness of a process. When the process is
optimal, the reaction is quantitative; the yield is 100%.
actual yield
percentage yield = x 100
theoretical yield
Question:
The reaction in solution of sodium carbonate Na 2 CO 3 (aq) with nickel (II) chloride NiCl 2 (aq)
produces sodium chloride NaCl (aq) and a precipitate of nickel (II) carbonate NiCO 3 (s).
• First balance the chemical equation.

• If 2.12g of sodium carbonate reacts with an excess of nickel chloride, what will be the
maximum amount of nickel carbonate produced?
• If the reaction only yield 1.85g of sodium carbonate; what is the percentage yield of
the reaction.
Answer:
• First balance the sodium Na, second the carbonate CO 3 , then the nickel Ni and check
the balance of chloride.
Na 2 CO 3 (aq) + NiCl 2 (aq)  NiCO 3 (s) + 2 NaCl (aq)
• 2.12 g Na 2 CO 3 is 0.02 mol  produces 0.02 mol NiCO 3

1 mol NiCO 3 has mass 118.7 g mol-1: 0.02 mol has mass 2.37 g
100% yield of NiCO 3 is 2.37 g
• Maximum mass of NiCO 3 is 2.37 g

Yield = (mass found/maximum mass) x 100 = (1.85/2.37) x100 = 79.7%
When one reagent is added in excess; the reaction yield is calculated based on the limiting
reagent.
Limiting reagent is the reagent that will be totally consumed when the chemical reaction is
complete.
Exercise: Magnesium metal reacts with chlorine gas to give magnesium chloride. We
prepare a reaction using 1 g of magnesium and 4 g of chlorine. Which reagent is in excess,
and by how much?
• First write the balanced chemical equation
Chemical equation Mg (s) + Cl 2 (g)  MgCl 2 (s)

Molar mass 24.3 g 70.9 g 95.2 g
From the chemical equation: one mole of magnesium reacts with one mole of chlorine.
Note. Always work in moles of reagents.

• calculate the quantity of magnesium in the reaction (in mole)

n = m/M , number of mole of magnesium n Mg = 1/24.3 = 0.041 mole
• calculate the quantity of chlorine Cl 2 in the reaction

n = m/M , number of mole of chlorine n Cl2 = 4/70.9 = 0.056 mole
Chlorine is in excess.
• calculate the quantity in excess :

n = 0.056 - 0.041 = 0.015 mol
Chlorine Cl 2 is in excess by 0.015 mol
The mass of the Cl 2 in excess is m = n . M ; m = 0.015 x 70.9 = 1.1 g
Example 2. Iron(III)oxide, Fe 2 O 3 (s) in powder reacts with aluminium powder, Al(s), to give
Iron, Fe (s) and aluminium oxide, Al 2 O 3 (s). If 8.0g of Al powder reacts with 12.0g of iron
oxide:
(a) Which reagent is in excess?
(b) By how much (in terms of mass and moles)?
(c) What is maximum yield of aluminium oxide (by mass)?
(d) If the yield of iron is 5.2g, what is the % yield of the reaction?

Answer
• First balance the chemical equation:
Fe 2 O 3 (s) + 2 Al (s)  2 Fe (s) + Al 2 O 3 (s)
Balance iron, then oxygen and end with aluminium
• Calculate the quantity (mol) of each reagent.
Using the formula m = n x M ; n = m/M ;

with n Al = 8.0 / 26.98 = 0.297 mol
and n Fe2O3 = 12.0 / 159.69 = 0.075 mol
From the chemical equation: 1 mol of Fe 2 O 3 reacts with 2 mol of Al
Then; 0.075 mol Fe 2 O 3 will react with 0.150 mol Al.
(a) Aluminium is in excess by n = 0.297-0.150 = 0.147 mol
Mass of aluminium in excess is m = 4.0 g
• The limiting reagent is Fe 2 O 3

1 mol Fe 2 O 3 produces 1 mol Al 2 O 3
0.075 mol Fe 2 O 3 produces 0.075 mol Al 2 O 3 at a maximum
m = 7.65g
• Maximum yield of Fe is 0.15 mol (since 1 mol Fe 2 O 3 produces 2 mol Fe) ≡

8.38g
• % yield of reaction is 5.2/ 8.38 x 100/ 1 = 62.1 %
1.2.6. Chemistry in Solution

A solution is made of solute dissolved in a solvent. The solution is defined as a
homogeneous mixture of one phase only.
Solvents can be liquid, solid or a gas.
Solute can be any substance dissolved in a solvent.

When water is the solvent the solution is called an aqueous solution.
The solutes dissolved in water are quantified by their concentration c in the solution: The
molarity is expressed by the quantity of solute (n) in mole per volume (V) in litre, the
molarity’s unit is: mol.l-1.
n (mol)
C=
V (Litre)

Exercise: What is the molarity of a solution of HCl if 1.0g of HCl gas is dissolved, producing
a volume of 100 mL?
Answer:
• calculate the quantity in mole of HCl in 100mL;
n = m/M
n = 1.0 / 36.45 = 0.027 mol
• Calculate the concentration of HCl per litre (100mL is 0.1L).

c=n/V
c = 0.027 / 0.1 = 0.27 mol L-1
Exercise: Calculate the mass of Na 2 CO 3 needed to prepare a 250 mL solution of

concentration 0.15 mol L-1?
• Use the formulae: m = n M and c = n/V to calculate the mass needed.
The second formula is expressed as n = c V
Mass is expressed as m = c V M
using c = 0.15 mol.L-1
V = 0.25 L
M Na2CO3 = 106.0 g.mol-1
m = 0.15 x 0.25 x 106.0 = 3.975 g
Note. Always check the units: volumes are in litre.
Ions in Solution
When ionic solids are dissolved in water, a phenomenon of solvation occurs: water
molecules form shell-layers around both anions and cations. Solvation stabilises the charges
of the ions and also separates the ions from each other.
NaCl(s) + n H 2 O  NaCl (aq) ≡ Na+ (aq) + Cl- (aq)
Spectator ions
A spectator ion is not modified by the chemical reaction and is found unchanged when the
reaction is complete. Spectator ions are identical on both side of the chemical equation (as
reagents and as products).
AgNO 3 (aq) + NaCl (aq)  AgCl (s) + NaNO 3 (aq)
Some ionic solid are solvated:
Ag+ (aq) + NO 3 - (aq) + Na+ (aq) + Cl- (aq) 

AgCl (s) + Na+ (aq) + NO 3 - (aq)
The ion nitrate, NO 3 -, and sodium, Na+ are unchanged by the reaction; they are spectator
ions.
The chemical equation can be simplified by removing the spectator ions:
Ag+ (aq) + Cl- (aq)  AgCl (s)

1.2.7. Types of Chemical reaction in Aqueous Solution

We will be looking at three types of reaction that occur in aqueous solution and for which we
will apply stoichiometry (quantitative chemistry) to solve problem.
Precipitation is the formation of a solid in solution. The solid formed is called the precipitate,
it could fall to the bottom of the solution or remain in suspension.
e.g. Precipitation of barium sulfate in water. Barium chloride in solution reacts with sodium
sulfate in solution to give a precipitate of barium sulfate and sodium chloride in solution.
BaCl 2 (aq) + Na 2 SO 4 (aq)  BaSO 4 (s) + 2 NaCl (aq)
The chemical equation can be simplified by removing the spectator ions:
Ba2+ + SO 4 2-  BaSO 4 (s)
Note. The reaction of precipitation is driven by the solubility of ions: barium chloride, sodium
sulfate and sodium chloride are water soluble and the ions barium Ba2+, chloride Cl-, sodium
Na+ are solvated. Barium sulphate is insoluble in water.
Precipitation/dissolution
Ionic solids dissolve when the attraction between constituent ions and the water molecules
are stronger that the ionic bond of the ionic solid.
As a general observation: salts from lithium Li+, sodium Na+, potassium K+, ammonium NH 4 +
are very soluble as these small cations are strongly solvated by water.
Salts of nitrate NO 3 - are also very soluble.
Acid/base reactions.
Because an Acid can be defined either as a proton donor or as an electron acceptor; there
are two definitions of acid/base reaction.
According to the Brǿnsted-Lowry (B-L) definition an acid is a donor of proton (H+) and a
base is an acceptor of proton. Acid/base reaction thus is an exchange of proton.
e.g HCl (aq) + NaOH (aq)  NaCl (aq) + H 2 O (l)

HNO 3 (aq) + NH 3 (aq)  NO 3 - + NH 4 +
B-L Acids B-L Bases B-L Bases B-L Acid
According to the Lewis definition an acid is an acceptor of an electron pair and a base is a
donor of an electron pair. An acid/base reaction thus is an exchange of an electron pair
where a Lewis base donates an electron pair to a Lewis acid to form a Lewis adduct by
covalent bond formation.
e.g. NH 3 (aq) + Ni2+  Ni(NH 3 ) 6 2+ (aq)

Lewis Base Lewis Acid Lewis Adduct

Strong and weak Brǿnsted-Lowry Acids and Bases.

Strong acids react completely with H 2 O to give solvated hydronium H 3 O+
Strong bases react completely with H 2 O to give solvated hydroxide OH-
Weak acids and bases only partially react with water and the formation of hydronium and
hydroxide ions are reversible reactions.
Hydronium H 3 O+ is the strongest acid that can stay un-dissociated in water – any stronger
acid will totally dissociate in water. All weaker acids can stay in water and will be only
partially dissociated.
The stronger the acid the more dissociated it is in water.
e.g. Ethanoic acid: only about 0.4% of the acid is dissociated in water; that is four
molecules every 1000.
-
CH3CO2H (aq) + H2O CH3CO2 + H3O+
Hydrogen cyanide : only about 1 molecule in every 1,000,000 is dissociated in water.
HCN (aq) + H2O CN - + H3O+
The strength of an acid in water is always relative to the strength of the acid hydronium
H 3 O+: the stronger the acid the stronger the shift of the chemical equilibrium to the right hand
side.
H-X (aq) + H2O (l) H3O+ (aq) + X- (aq)
Relative strength of acids:

e.g. the Hydrogen halides HX. HF << HCl < HBr < HI ,
The strength of acidity follows the trend in bond dissociation energy (B.D.E.) of the H-X
bond. The weaker the H-X bond the stronger the acid. In this series HI is the strongest acid.
We note that the acidity also follows the size of the Halide; the bigger the halide the weaker
the H-X bond.
B.D.E. is energy of the reaction: H-X (g)  H+ (g) + X- (g)

Hydrogen halide (acids) Bond Dissociation Energy (kJ mol-1)

H-F 567
H-Cl 431
H-Br 366
H-I 298
When the size of atoms is similar we note a link between polarity and acidity. The more polar
the H-X bond (the more ionic) the stronger the acid.
H-Cl is a stronger acid that H-SH
Oxo-acids are polyatomic ions with polar hydrogen-oxygen bonds that can be broken to
form ions. Oxo-acids can lose one or more protons (from H-O bond breaking).
They contain: oxygen

at least one other element
at least one hydrogen bond to an oxygen atom
e.g.: Nitric acid HNO 3 , sulfuric acid H 2 SO 4 , chloric acid HClO 3 , phosphoric acid H 3 PO 4

When comparing the relative acidity of oxoacids:

• The more polar the H-O bond the stronger the acid
• The greater the electron withdrawing effect on the oxygen bonded to the proton, the
stronger the acid.
The two main factors that affect the acidity of oxoacids:

• The electronegativity of the central atom
• The number of other oxygen atoms bonded to the central atom
e.g.: H 2 SO 3 is more acidic than H 2 SeO 3 - S more e/neg than Se

H 2 SO 4 is more acidic than H 2 SO 3 - more O atoms
Redox reactions are reactions involving electron transfer between species.

During a redox reaction, oxidants are reduced (they gain electron(s): their oxidation states
decrease) and reducers are oxidised (they lose electrons: their oxidation states increase).
• Reduction is the gain of electron (oxidation state decrease).

• Oxidation is the loss of electron (oxidation state increases).
• Reducing agent or Reducer gives electron(s) (Reducer is Oxidised)
• Oxidising agent or Oxidant accepts electron(s) (Oxidant is Reduced)
Example of redox reaction using oxidation states:
2 Na + F 2  2 NaF
Sodium metal (0) is oxidised into sodium cation Na+(I)

Fluorine gas (0) is reduced to fluoride F- (-I)
Note. Redox equations must be balanced so that the number of electrons given by the
reducer equals the number of electrons accepted by the oxidant. Balanced redox equations
do not leave any electrons free.
The oxidation state (or oxidation number) in bracket is an indicator of the oxidation
degree of an atom. It is defined as the calculated charge an atom would have when
electrons are counted according to the following 5 rules:
1. The oxidation number of a free element is zero (0).

2. The oxidation number of a monoatomic ion is equal to the net charge on the ion.
3. The sum of all the oxidation numbers in a neutral molecule must equal zero. The sum
of all the oxidation numbers in an ion must equal the charge of the ion.
4. Fluoride compounds; F has an oxidation number of (–I). Oxides compounds: O
generally has an oxidation number of (–II) (with few exceptions such as when oxygen
is bound to another oxygen like in hydrogen peroxide H-O-O-H).
5. The oxidation number of a proton (H+) is one (I) and a hydride anion (H-) is minus
one (-I). The oxidation state of atomic hydrogen (H) and hydrogen gas (H 2 ) is zero
(0).

Example. Fe 2 O 3
• Each oxygen is (-2), the total oxidation number of all the oxygens is: -6
• The compound is neutral; so the total oxidation number of the two irons has to be +6.
Therefore each iron has an oxidation number (+3).
Example. H 2 SO 4
• Each proton is (+1): total for all hydrogens = +2
• each oxygen is (-2): total for all oxygens = -8
• The compound is neutral; so the oxidation number of Sulfur is (+6)
When an element gives one electron, it gives away one negative charge and its oxidation
number is increased by one unit. Oxidation sates are noted “+n or -n” to distinguish them
from the charge noted: n+ or n-.
Example. 2 KCl + MnO 2 + 2 H 2 SO 4  K 2 SO 4 + MnSO 4 + Cl 2 + 2 H 2 O

(+1 -1) (+4 -2) (+1 +6 -2) (+1 +6 -2) (+2 +6 -2) 0 (+1 -2)
K+ unchanged, O2- unchanged, H+ unchanged, S6+ unchanged

Cl goes from -1 to 0  loses e-, so Cl- is oxidised
Mn goes from +4 to +2  gains e, so Mn4+ is reduced
Balancing Redox Equation, in three steps:

• separate the two processes of oxidation and reduction into two half-equations
• balance each half-equation separately. Balance oxygen atoms with H 2 O or OH-
(depending on the availability) and balance the protons with H+, eventually balance
the charges with e-.
• balance the electrons of each half-equation and combine them into the whole redox
equation.
Redox reaction may be dependent on pH, as H+ or OH- and H 2 O often play crucial roles in
the redox process.
Example. Reaction of permanganate MnO 4 - with iron (+2) Fe2+

• In acidic condition (low in [OH]-):
MnO4- + Fe
2+
Mn2+ + Fe3+
• Separate into two half-equations: calculate the oxidation number of manganese and
iron. Manganese is reduced; its oxidation number decreases from +7 to +2. Iron is
oxidised: its oxidation number increases from +2 to +3.

MnO4
- Mn2+
+7 +2
Fe2+ Fe3+
+2 +3
• balance each half equation separately. Balance oxygen atoms with H 2 O, then the
hydrogen atoms with H+. Balance the charge at the end with electron(s).
MnO4- + 8 H+ + 5 e- Mn2+ + 4 H2O

+7 +2
Fe2+ Fe3+ + e-
+2 +3
• balance the number of electrons and combine the two half-equations into the whole
redox equation. Eliminate the common factors from each side.
MnO4- + 8 H+ + 5 e- Mn2+ + 4 H2O

+7 +2
5 Fe
2+
5 Fe3+ + 5 e-
+2 +3
MnO4- + 8 H+ + 5 Fe2+ Mn2+ + 5 Fe3+ + 4 H2O
• In basic condition (aqueous solution high in [OH]-):
MnO4- + Fe
2+ 3+
MnO2 + Fe
• calculate the oxidation number of manganese and iron:

-
MnO4 MnO2
+7 +4
2+ 3+
Fe Fe
+2 +3
• balance each half equation separately. Balance oxygen atoms with OH-. Balance
hydrogen atoms with H+ (and remember in basic condition, H+ + OH- give H 2 O: so
add OH- to both side of the equation to remove H+ from the left hand side of the
equation. Then balance the charge at the end with electron(s). Combine the two
half-equations into one redox equation.
- + -
MnO4 + 2H + 2OH- + 3e -
MnO2 + 2 OH + 2 OH-
+7 +4
- - -
MnO4 + 2 H2O+ 3e MnO2 + 4 OH
+7 +4
2+ 3+ -
3 Fe 3 Fe +3e
+2 +3
- 2+ 3+ -
MnO4 + 2 H2O + 3 Fe MnO2 + 3 Fe + 4 OH

27
TOPIC 2. ATOMIC STRUCTURES AND ORBITALS
Topic 2
Atomic Structures and Orbitals
Contents
2.1. INTRODUCTION .................................................................................................. 28
2.1.1. The Rutherford experiment ...................................................................... 28
2.1.2. Isotopes.................................................................................................... 29
2.2. THE BEGINNING OF QUANTUM THEORY ................................................................ 30
2.2.1. Wave-particle duality of light .................................................................... 30
2.2.2. Atomic spectroscopy. ............................................................................... 33
2.2.3. The atomic theory of Niels Bohr (1885-1962) ........................................... 34
2.2.4. The limitations of the Bohr model ............................................................. 35
2.3. QUANTUM (W AVE) MECHANICS .......................................................................... 36
2.3.1. Heisenberg’s uncertainty principle............................................................ 36
2.3.2. Schrödinger’s wave equation ................................................................... 36
2.3.3. Quantum numbers.................................................................................... 36
2.3.4. Pauli exclusion principle ........................................................................... 38
2.4 MORE ABOUT ATOMIC ORBITALS .......................................................................... 38
2.4.1. Electronic density ..................................................................................... 39
2.4.2 Depicting Atomic Orbitals .......................................................................... 39
2.4.2. Atomic Orbital Size ................................................................................... 41
2.4.3. Atomic Orbital Energy .............................................................................. 42
2.5. THE PERIODIC TABLE ......................................................................................... 44
2.5.1. Core and Valence Orbitals and Electrons ................................................ 45
2.5.2. Periods and Groups ................................................................................. 45
2.5.3. Periodicity in Atomic Properties ................................................................ 47
Learning objectives
• Atomic Structure – Electromagnetic radiation ; quantization of energy ; the photon
; atomic line spectra ; the hydrogen atom ; wave properties of the electron ; wave
mechanical view of the atom ; quantum numbers and atomic orbitals ; orbital
shapes.
• Electron Configurations and Periodicity – electron spin ; Pauli exclusion principle ;
orbital energies and electron assignments ; electron configurations ; atomic
properties and periodic trends ; atomic size ; ionization energy ; electron affinity.

28
2.1. Introduction
2.1.1. The Rutherford experiment
Before the Rutherford experiment, the prevailing model for the atom was the plum pudding
model: atoms were thought to be made of negative corpuscles (electrons) floating in a soup
of positive charges. Rutherford set up an experiment to test the model: a beam of alpha
particles was aimed at a piece of gold foil that was only few atoms thick. If the model was
correct, all the alpha particles would have passed straight through the foil.
He observed that although most particles passed through the foil, a small portion of particles
were deflected by about one or two degrees and about one particle in every 20,000 was
deflected by 90 degrees and more. Some particles even bounced back at the source.
The Rutherford experiment demonstrated the existence of the atomic nucleus; as a small,
positively charged entity placed at the center of the atom and concentrating most of the atom
mass.
The experiment also gave information on the relative size of nucleus and atom and on the
nucleus mass. Rutherford was able to calculate the size of the gold atom as 1.35 x10-10 m
diameter and the size of its nucleus as 7 x 10-15 m diameter (20,000 times smaller!)
The atomic nucleus is made of two types of nucleon particles: positively charged proton (p)
and uncharged neutron (n). Proton and neutron make most of the atom’s mass. The protons
are positively charge and make up the charge of the nucleus. The atomic number Z is the
number of protons in the nucleus.
Electrons are negatively charged. Each electron can neutralize the charge of one proton.
Neutral atom. When the number of electrons equals the number of protons (Z = n e-).
Anion. When the number of electrons is higher than the number of protons the atom is
negatively charged (Z < n e-).
Cation. When the number of electrons is lower that the number of protons the atom is
positively charged (Z > n e-).
Note. When calculating the mass of an element; the mass of the proton and neutron are
added and the mass of the electrons is generally ignored.

29
Charge in coulombs (C) Mass (kg) Mass (u)
Proton +1.6022×10−19 1.6726×10−27 1.0073
Neutron 0 1.6749×10−27 1.0086
electron −1.6022×10−19 9.1094×10−31 5.4858×10−4
Any atom can be written:

X is the Chemical Symbol of the Element.
A
A is the mass number (number of nucleons).
Z
X Z is the atomic number (number of protons).
An element X is characterised by a number of protons Z (the atomic number) and identified

by its chemical symbol X. One element can have several isotopes.
2.1.2. Isotopes.
Atoms have the same number of protons Z therefore share the same chemical symbol X, but
have a different number of neutrons (thus a different mass number A).

30
2.2. The Beginning of Quantum theory

The Rutherford model describes the nucleus in an electron cloud but is not suitable to explain
the observed emission spectrum of atoms. Niels Bohr proposed a model describing more
precisely the electrons in orbits around the nucleus. In the Bohr model, electrons reside in
orbits of defined energy levels and can move from one orbit to another gaining or loosing a
discrete amount of energy. The quantum theory was born.
2.2.1. Wave-particle duality of light

When light interacts with large object such as prism or diffraction grating the wave properties
dominate. However when light interacts with small objects such as electrons it shows the
behavior of a particle (a photon). Scientists were strongly divided over the nature of light: for
some light was an electromagnetic wave and to others it was made of particles. Einstein
combined both sides in a unified equation taking account of the wave-particle duality of light.
• Light is characterized by wave parameters such as wavelength, frequency, speed and

amplitude.
wavelength, λ
Amplitude
Amplitude
time (s)
1 second
Frequence ν = 5 Hz or (5 s-1)
• Wavelength: λ in m e tre (m ) is the dis ta nce be twe e n two wa ve cre s ts.
• Frequency: ν in (s-1 or Hz) is the number of wave crests that pass over one point
every second.
• Speed (celerity) c in meter per second (m.s-1). Light, like all electromagnetic
radiations travels through vacuum at a speed of c = 2.998 x108 m.s-1
c=νλ
• Amplitude: A is the height of wave.

31
Phase: Constructive interference: waves (a) and (b) are in phase; the resulting amplitude is
the sum of the individual magnitudes. Destructive interference: (a) and (b) are completely out
of phase; the resulting amplitude (the sum of the waves) is zero (a + b = 0).
Resultant wave
wave (a)
wave (b)
Constructive interference Destructive interference
Exercise. Interconverting wavelength and frequency.

Calculate the frequency of a red light with a wavelength of 680 nm.
Note. A nanometer (nm) is 10-9 meter.
Answer. Using the formula: frequency ν = c / λ

= 2.998 x 108 / 680 x 10-9
= 4.4 1014 Hz
Colour Violet blue green yellow orange Red

Frequency
range 7.7 – 6.8 6.8 - 6.1 6.1 – 5.3 5.3 - 5.1 5.1 - 4.8 4.0 - 4.8
(1014Hz)
Wavelength
range 440 - 390 490 - 440 565 - 490 590 - 565 625 - 590 740 - 625
(nm)
The human eyes are only receptive to a relatively small range of wavelengths (from 390 to
740 nm); visible light is a small part of the full electromagnetic spectrum that span from the

32
gamma rays (with picometer (10-12 m) wavelength) to the long radio wave (100 m
wavelength).
• Planck's constant
When classical physics was applied to the light emissions of the sun, it successfully
predicted the intensity of emissions at low frequency but vastly overestimated the
high frequency emission: predicting infinite intensity for the very high frequency. That
was known as the “Ultraviolet Catastrophe” and was in contradiction with the
observed radiation emission spectrum.
In 1901 Max Planck solved the problem by introducing the idea of quantization. He
proposed that electromagnetic radiations could only be emitted or absorbed in
bundles or quanta of radiation (they were later called photons) of energy proportional
to the frequency. He introduced the proportionality constant h (Planck's constant)
between the energy (E) of a photon and the frequency ν of its associated
electromagnetic wave.
The energy of one photon is calculated in Joule (J) with the Planck's relation:
-34
Where h is the Planck's constant, h = 6.626 x 10 Js
E=hν -1
and ν is the frequency in Hz (s )
• The photoelectric effect. When light of high enough frequency is shone onto a metal
in vacuum: electrons are emitted from the metal. Below a certain frequency (called
the threshold frequency ν 0 ) no electron are emitted - regardless of the light intensity.
Above the threshold frequency electrons are emitted even when the light is not very
intense.
Scientists could not understand why low frequency high-intensity light would not
cause electrons to be emitted while higher frequency low intensity light would.
In 1905 Albert Einstein published a paper explaining the photoelectric effect. He

proposed that the energy from photon (described by Planck) is exchanged only in
discrete amounts (quanta) and can be transferred onto the metal's electrons which
are then ejected from their orbit.
• Photons have no mass but have frequency ν and energy E.

• If E < h ν 0 (ν < ν 0 ): no electrons are ejected
• If E = h ν 0 (ν = ν 0 ): electrons are ejected
• If E > h ν 0 (ν > ν 0 ): electrons are ejected with a kinetic energy KE, any excess of
energy passed to the electron in the form of KE.

33
• When light intensity increases more electrons are ejected and when the frequency
increases the ejected electron get more kinetic energy KE.
• The minimum energy required to eject electrons is the binding energy or work function
Φ and depends on the metal.
Where h is the Planck's constant, h = 6.626 x 10-34 Js

Φ = h ν0
and ν0 is the threshold frequency in Hz (s-1)
2.2.2. Atomic spectroscopy.

As light interacts with atoms: light is absorbed and/or emitted by the electrons of atoms;
revealing details about the electron's energy levels and about the electronic structure of the
atoms.
Light spectrum. When the sun light passes through a prism it is dispersed into a continuous
spectrum of wavelengths (the rainbow).
Absorption spectra. When the sun light is first filtered through a tube containing atoms of
gases, some wavelengths are selectively absorbed by the atoms, leaving dark lines known as
absorption lines in the spectrum.
Emission spectra. When the atoms of gases contained in a tube are heated they glow, the
atoms emit light at certain wavelengths, showing colored lines known as emission lines in the
spectrum.
Emission spectrum of hydrogen.

34
2.2.3. The atomic theory of Niels Bohr (1885-1962)

The Bohr model explains the absorption and emission spectrum of hydrogen. The model
which was first developed for the hydrogen like atoms (atom with one electron) is based on
four postulates:
1) An electron in an atom moves in a circular orbit around the nucleus under the
influence of the Coulomb attraction between the electron and the nucleus, obeying the
laws of classical mechanics.
2) An electron can only move in an orbit for which its orbital angular momentum L is and
integral multiple of h/2π.
3) An electron moving in such an allowed orbit does not radiate electromagnetic energy.
Thus, its total energy E remains constant.
4) Electromagnetic radiation is emitted if an electron, initially moving in an orbit of total
energy E i , discontinuously changes its motion so that it moves in an orbit of lower
total energy E f . The frequency of the emitted radiation  is equal to the quantity (E i -
E f ) divided by h.
-RH En energy of electron in orbit n (En is negative)

En = RH Rydberg constant for H atom (2.179 x10-18J)
n2 n principal quantum number
• Energy of electron in an orbit is conventionally negative
• Energy of a free electron at rest is zero: E = 0
• Energy of an electron in motion is positive: E = h ν
The emission spectrum of the hydrogen atom is divided into spectral series according to the
energy level to which the electrons move down. The first three series are called Lyman (n=1),
Balmer (n=2) and Paschen (n=3).
The Lyman series is due to electronic transitions from higher energy levels to n = 1; the
wavelengths of the emissions are in the ultra-violet region (short wavelength; high energy).
The Balmer series is due to electrons from higher energy levels (n = 6, 5, 4, 3) moving to the
level n = 2; the wavelengths of the emission associated with these transitions are within the
region of visible light.

35
The Paschen series is due to the electron transitions from higher levels to n = 3. The
wavelengths of the emissions are in the infra-red region (long wavelength, low energy).
Emission spectrum of hydrogen atom
Figure. Electron transitions and the associated wavelengths of emission.
2.2.4. The limitations of the Bohr model

The Bohr model is based on a simple hydrogen-like atom with only one electron in orbit. It
successfully established the concept of the quantisation of atomic energy levels but was not
detailed enough to explain the emission spectra of heavier atoms.
The Bohr model assumes that electrons are particles.
In 1923, de Broglie proposed that the concept of the wave-particle duality of light could be
extended to electrons and devised an equation linking mass with particle wavelength.
λparticle = particle's wavelength (m)

h 2 -1
h = Planck's constant (Js) or (m Kg s )
λparticle =
mu m = particle's mass (Kg)
-1
u = particle's velocity (ms )
• Calculate the wavelength of a cricket ball, m = 0.2 Kg, u = 30 ms-1,
h = 6.626 10-34 Js.
λ cricket ball = 1.10 x 10-34 m (undetectable)
• Calculate the wavelength of an electron, m = 9.1094×10−31 Kg , u = 105 ms-1,
λ electron = 7.3 x 10-9 m (7.3 nm should be detectable)
In 1927, the wave properties of electron were confirmed when a beam of electron was
diffracted (just like light) by a crystal.

36
2.3. Quantum (Wave) Mechanics
The De Broglie equation applies to free electrons, not to the electrons in atomic orbits.
2.3.1. Heisenberg’s uncertainty principle

It is impossible to know simultaneously the position and the momentum of an electron. The
greater the certainty in position the greater the uncertainty in momentum and vice versa.
2.3.2. Schrödinger’s wave equation

Schrödinger formulated a theory to describe the electrons in atoms and molecules using the
wave properties of the electrons. His approach was to use a standard wave equation with
replacement of the trajectory component (that contains electronic position and motion) by
wavefunctions ψ .
The time-independent Schrödinger wave equation describes standing waves, called

stationary states (or orbitals).
ψ : wave-function (stationary wave – orbital).

ĤΨ=EΨ E : energy of an orbital ψ is the proportionality constant.
Ĥ : Hamiltonian operator (time independent).
2.3.3. Quantum numbers

Solving the Schrödinger wave equation gives a set of quantised orbitals (wavefunctions
ψ) each characterized by its energy and by 3 quantum numbers: principal (n), azimutal or
angular (l) and magnetic (m l ).
• Principal quantum number n. n is an integer (n = 1, 2, 3, 4, etc…), n defines the
size and the energy of the orbital (an electron shell).
• Azimutal quantum number l, can be any number between 0 and (n-1). (l = 0, 1, 2,
(n-1)), l defines the shape of the orbital (electron sub-shells).
Example with n = 3: l can be 0, 1 or 2.

n = 3, l = 0 n = 3, l = 1 n = 3, l = 2
(spherical orbital 3s) (dumbbell orbital 3p) (cloverleaf orbital 3d)

37
• Magnetic quantum number m l . can be any number between –l and +l. (m = -l, -(l-1),
…0, …, (l-1), l. m l defines the orientation of the orbital.
Example with l = 1 (orbital p): m 1 can be = -1, 0, 1.

m 1 = 1 (orbital p x ) m 1 = 0 (orbital p z ) m 1 = -1 (orbital p y )
z
y
x
Naming atomic orbitals using quantum numbers n, l, m l :

n = 3, l = 0, m l = 0: 3s
n = 3, l = 1, m l = 0: 3p z
n = 3, l = 2, m l = -1: 3d yz
Possible atomic orbitals:

n = 1: 1 atomic orbital: 1s
n = 2: 4 atomic orbitals: 2s, 2p y , 2p z , 2p x
n = 3: 9 atomic orbitals: 3s, 3p y , 3p z , 3p x , 3d xy , 3d yz , 3d z 2, 3d xz , 3d x 2 -y 2
n = 4: 16 atomic orbitals: 4s, three 4p, five 4d, and seven 4f.
• Spin quantum number m s can be + ½ or -½. ms describes the electron spin.

Electrons also have the further property of spin that can occur in two ways.
Notation: ms = +½ is noted ↑; ms = -½ is noted ↓.
Every electron in an atomic orbital can be described by a unique set of four quantum
numbers: three quantum numbers describing the orbital and one describing its spin.

38
2.3.4. Pauli exclusion principle

Each electron is described by a unique set of four quantum number: n, l, m l , m s .
The Pauli exclusion principle states that: no two electrons in the same atom can have an
identical set of four quantum numbers:
• Every electron is described by a unique set of four quantum numbers.
• There can’t be more than two electrons per atomic orbital.
• Two electrons occupying the same atomic orbital have opposite spin.
Maximum number of electrons per electron shell:

• First shell n =1 2e (in one orbital)
• Second shell n=2 8e (in four orbitals)
• Third shell n=3 18 e (in nine orbitals)
• Fourth shell n=4 32 e (in sixteen orbitals)
2.4 More about Atomic Orbitals

The chemical behaviour of atoms is determined by their electrons. The two most important
properties of the electrons in atoms are:
(i) the energy of their orbital (described by the principal quantum number (n) ) and
(ii) the spatial distribution of the electron density in the orbital (described by the
azimutal (l), and magnetic (m l ) quantum number.
Atomic orbitals are wavefunctions , and as wave have phase + or -.
Wave functions of hydrogen:
1s 2s 3s
Ψ 1s is + Ψ 2s is + inside and - outside Ψ 3s : + inside then - then + outside
One radial node Two radial nodes
Figure. Plotting the amplitude of Ψ versus the distance from the nucleus in ao units (Rho).

39
The unit of distance rho, radius of atomic orbital: a o = 1 is defined as the distance from
the nucleus at which the probability of finding the electron in a hydrogen atom is the
maximum. (0.53 x 10-10 m)
2.4.1. Electronic density

The electrons in Atomic orbitals are described via their wave properties; they are not
localized like a particle would be. To get an idea about where electrons are around the
nucleus; we use the radial distribution function, 4πr2Ψ2, which is the probability of finding an
electron at any point.
Although the amplitude of the wave function can be positive of negative, the radial distribution
function is always positive.
Figure. Plotting the radial distribution (electron density) function 4πr2Ψ2 versus the distance
from the nucleus in ao units (Rho). The vertical lines mark the 90% probability limit of finding
electron.
2.4.2 Depicting Atomic Orbitals

Atomic orbitals can be represented by their electronic density functions, either as a plot of
electron density versus radius or as a cross section. The best way to represent an atomic
orbital is a surface that defines a space within which there is a 90% probability of finding an
electron.
• s-orbitals are represented as spheres:
1s (+) 2s (-)
Figure. 1s and 2s-orbitals. The sign of the outer part of the wave function is represented in
shade (+) of white (-). The 2s-orbital has a radial node that is not represented: only the sign
of the outer part of the wave function is represented.

40
• 2p-orbitals have an angular node:
+
angular node or
-
Figure. 2p-orbitals have an angular node
• 3p-orbitals have a radial and an angular node
- radial node
+
angular node or
-
+
Figure. 3p-orbital 3p (n = 3, l = 1): (l) = 1 angular node; (n-1-l) = 1 radial node.
Radial and Angular Nodes.

• The number of angular nodes in an orbital is determined by the azimutal quantum
number l. (l = 1; 1 angular node).
• The total number of nodes in an orbital is = n-1.
• The number of radial nodes in an orbital is the total number of nodes – the number of
angular nodes. (n radial node = n - 1 - l)

41
Example of 3d-orbital. (n = 3; l = 2). The number of angular nodes is 2. The total number of
nodes is n-1 = 2. Thus 3d-orbitals have no radial nodes.
+ -
two angular nodes or
- +
dyz
two angular nodes or
dz2
2.4.2. Atomic Orbital Size

The principal quantum number n determines the size of the atomic orbital.
• The size increases with n.
• Atomic orbitals of the same shell (same n) have a similar size.

42
2.4.3. Atomic Orbital Energy

• For hydrogenoids (i.e. atoms with one electron):
-RH En energy of electron in orbit n (En is negative)

En = RH Rydberg constant for H atom (2.179 x10-18J)
2
n n principal quantum number
Formula deduced by Niels Bohr from the analysis of hydrogen spectra. The formula was later
confirmed by the solution of Schrödinger wave equation for the hydrogen atom.
Energy of the first orbital: E 1s (n=1).

E 1s = -2.179 x 10-18 J (energy per atom)
E 1s = -2.179 x 10-18 J x N A = -1312 KJ mol-1 (energy per mol)
Avogadro’s constant N A = 6.022 x1023 mol-1
Energy of the second orbital: E 2s (n = 2)

E 2s = -328 KJ mol-1
Energy of the third orbital s: E 3s (n = 3)

E 3s = -146 KJ mol-1
Energy level diagram of hydrogenoids (atoms with one electron only).
Orbitals from the same electron shell have identical energy: they are degenerate.
E 4s = E 4p = E 4d = E 4f
E 3s = E 3p = E 3d
E 2s = E 2p
2
En energy of electron in orbit n (En is negative)
-Z RH
Z nuclear charge
En = -18
n2 RH Rydberg constant for H atom (2.179 x10 J)
n principal quantum number
General formula given by the solution of the Schrödinger wave equation for other
hydrogenoid species, such as He+.
The increasing charge of nucleus stabilises and contracts the orbital.

E 1s in He+ < E 1s in H
Radius of He+ 1s-orbital < radius of H 1s-orbital

43
• Multi-electron species (shielding and penetration)
Shielding. Considering a free electron approaching a cation, He+: the electron is attracted by
the charge (2+) of the nucleus and experience the repulsion of the electron (1-) already in
orbit.
• The approaching electron is shielded from the nucleus by the electron already in the
orbital.
• The approaching electron experiences a reduced nuclear charge: the effective charge
Z eff < Z.
The effects of shielding can be calculated via the ionization energy E i .
Ionisation energy. Is the energy required to remove an electron from the atom (E i = lE ao l).
The greater the attraction with the nucleus the greater the E i of an electron.
Measured E i of electron Effective nuclear charges (calculated Z eff )
H 1312 kJ mol-1 Z eff (1s) = 1 = Z no shielding
He+ 5248 kJ mol-1 Z eff (1s) = 2 = Z no shielding

He 2373 kJ mol-1 Z eff (1s) = 1.34 < Z poor shielding
Li2+ 11815 kJ mol-1 Z eff (1s) = 3 = Z

Li+ 7298 kJ mol-1 Z eff (1s) = 2.36 < Z
Li 520 kJ mol-1 Z eff (2s) = 1.26 < Z shielding by two core electrons
The effect of shielding on the energy levels of atomic orbitals.

Considering the first ionization energy of lithium; the core electrons (electrons of the 1st
electron shell) have a strong shielding effect on the electrons of the second shell.
Four atomic orbitals are available for the outer shell electrons: one 2s-orbital, and three 2p-
orbitals. The electron will populate the most stable orbital. i.e.: the orbital with the greater Z eff
and the greater nuclear penetration.
From the electron density function diagrams; the 2s-orbital is more penetrating than a 2p-
orbital, therefore an electron in 2s-orbital will be more stable than one in a 2p-orbital. As a
result, the second shell atomic orbitals are not degenerate (2s ≠ 2p).
As a result the ground state configuration of lithium is 1s2 2s1

44
For atomic orbitals of the same level (same principal quantum number n)
• The smaller the azimutal quantum number (l), the more penetrating the orbital
• Electrons in s-orbitals are more stable that electrons in p, d or f orbitals
• For hydrogenoid species, there is no core electron effect hence the orbitals s, p, d, f of
the same shell are degenerate.
Looking at the Balmer series, we are considering the transition from levels n = 6, 5, 4, 3 to n
= 2 (l = -1, 0, 1). All electronic transitions are subject to the Laporte selection rule (∆l = +/-
1).
The emission spectrum of hydrogen. Since the orbitals are degenerate; only four
transitions are possible from levels n = 6, 5, 4 and 3 to level 2. As a result: there are 4 lines in
the emission spectrum of the hydrogen atom.
The emission spectrum of helium has many more lines. In helium, the s, p, d, f-orbitals are
not degenerate. According to Laporte rule (∆l = +/- 1), there are three possible transitions per
level: the electrons from level n = 6 to 3 can move from l value of: 0, 1, 2 to two different
levels in level n = 2 (l = 0 or 1): 24 electronic transitions are possible. That is 12 x 2 = 24
lines.
2.5. The Periodic Table
The Aufbau principle (from the German Aufbau: “construction, building up”) is used to
determine the electronic configuration of an atom molecule or ion in its ground state (i.e. in its
lowest possible energy). This principle guides the process by which the electronic structure of
an atom is built by progressively adding electrons with each successive electron filling an
available orbital of the lowest possible energy.
Hund’s rule. For degenerate atomic orbitals, the ground-state electronic configuration is that
with the greatest number of parallel spins
The Madelung energy ordering rule. The order in which the orbitals are filled is given by
the n+l rule. Orbitals with a lower n+l value are filled before those with higher n+l values (n
and l are the principal and the azimutal quantum numbers respectively). When two orbitals
have identical n+l values; the orbital with a lower n value is filled first.
Note. The Madelung rule is an empirical rule, based on observation. It therefore reflects
almost all experimental electronic configuration, but not all. For example, with the transition
metals Cr and Cu, the energy of the 3d level (n+l = 5) is in fact lower than that of the 4s (n+l =
4).

45
2.5.1. Core and Valence Orbitals and Electrons

Valence electrons reside in the outer atomic orbital, the “valence orbital” and are available
for bonding and chemical reactions. They are responsible for the shapes of molecules. The
number of valence electrons possessed by an element determines its group in the Periodic
Table – elements of the same group have the same number of valence electrons.
Core electrons occupy the inner orbitals and are not generally available for bonding. Core
electrons are responsible for the shielding effect.
2.5.2. Periods and Groups

The form of the Periodic Table is closely related to the electronic configuration of the
elements. The elements of the same group have the same number of valence electrons.
Group name number of configuration

valence of valence electrons
electrons
1 Alkali metals 1 ns1
2 Alkaline earth metals 2 ns2
15 Pnictogens (nitrogen group) 5 ns2np3
16 Chalcogens (oxygen group) 6 ns2np4
17 Halogens 7 ns2np5
18 Noble gases 8 ns2 np6

(except He: 2) (except He: 1s2)
The blocks of the Periodic table

Group Name Valence electrons
number configuration
1-2 s-block 1-2 ns1 and ns2
13-18 p-block 3 -8 group 13: ns2np1
group 18: ns2np6
3-12 d-block or (transition metals) 3-12 Sc: 3d14s2 to
Zn: 3d104s2

46
Configuration of the transition metal cations.

The elements of the transition metal group tend to lose the valence electrons from their s-
orbital, plus one, two or more valence electrons from their d-orbital, forming various possible
cations.
+7
+6 +6 +6
+5 +5 +5 +5 +5
+4 +4 +4 +4 +4 +4 +4
+3 +3 +3 +3 +3 +3 +3 +3 +3
+2 +2 +2 +2 +2 +2 +2 +2 +2 +2
+1 +1
Sc Ti V Cr Mn Fe Co Ni Cu Zn
[Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar]
2 2 5 1
3d64s
1 2 3 2 5 2 2 7 2 8 2 10 2
3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d104s1 3d 4s
Oxidation states of the transition metal (first period), in bolded are the predominant oxidation states
• In transition metals, the 4s-orbital lies lower in energy and is more penetrating than
the 3d-orbitals. Thus, electrons fill the 4s-orbitals before the 3d-orbitals.
• When transition metal cations are formed, the 4s-electrons are removed first,
indicating that: in the cation the 4s orbital is higher in energy than the 3d-orbitals.
When electrons from the 4s orbital are removed, their shielding effect on the 3d-
orbitals is also removed. This results in increased stability of the 3d-orbitals (i.e.
lowering the 3d-orbital energy levels).
E E
3d
4s 4s
3d
2+
Fe Fe

47
Unexpected configuration
The 3d and 4s-atomic orbitals are close in energy and lead to the unexpected configuration
for Cr and Cu.
The electronic configuration for Cr is [Ar] 3d5 4s1 not [Ar] 4s2 3d4, because in Cr, the 4s-orbital
has higher energy than the 3d-orbital.
In Cu, the electronic configuration is [Ar] 3d10 4s1 not [Ar] 4s2 3d9, because the 4s-orbital in
Cu has a higher energy than the 3d-orbital.
Note. Need to know the position in the Periodic Table and the electronic configuration of the
first 36 elements (H-Kr) for year 1 examinations
Comment. Tungsten, symbol W (from the chromium group): has an expected electronic
configuration [Xe] 4f14 5d4 6s2 because the 6s-orbital has a lower energy than the 5d-orbitals
in this instance.
2.5.3. Periodicity in Atomic Properties

In the Periodic Table, the elements are organized according to their respective electronic
configurations. The trends in atomic properties of the elements are best described with
respect to the Periodic Table.
2.5.3.1. Atomic radius

The atomic radius is defined as the distance between the nucleus and the boundary of the
outermost occupied atomic orbital.
• Along the periods from left to right, the atomic radius decrease. This is due to the
increasing effective nuclear charge Z eff concentrating the electron clouds.
• Down the groups from top to bottom, the atomic radius increases. The number of
occupied orbitals increase and thus the atomic radius increases.
• Along the d-block the atomic radius is mostly constant. Since the 4s-orbital has a
strong shielding effect, Z eff does not increase significantly with an increase in the
nuclear charge Z.
2.5.3.2. First ionisation energy.

The first ionization energy E i1 is the energy necessary to remove one electron from the
outermost occupied orbital
Factor influencing the Ei1: shielding effect and orbital penetration.

• Along the periods, E i1 increases. As the effective charge Z eff increase the valence
orbitals are stabilised.
• Down the groups, E i1 decreases. The valence orbitals are less stable.
• Along the d-block E i1 is mostly constant. Due to the strong shielding effect of 4s
orbital, Z eff is nearly constant along the block and so is E i1 .

48
From H to He:
The electron in 1s orbital of He is not well shielded so Z eff is important and the electron is
strongly attracted by the nucleus.
From Li to Ne:
Be. The electrons in the 2s orbital are not well shielded so Z eff is important
B. The electron in the 2p orbital is strongly shielded by the penetrating and full 2s orbital. As a
result; the BE i1 is lower than the Be E i1 .
C to Ne. The electrons in the 2p-orbitals are not well shielded by other 2p electron(s); Ei1
increases from C to Ne.
O. THe O E i1 is lower than N E i1 . When the electron is removed from an O atom, the
remaining 2p-electrons can adopt a parallel spin arrangement which is more stable. Thus, the
ionization gives relief from electron pairing.
2.5.3.3. Electron affinity.

Electron affinity is the energy obtained when an electron is added to an atom in the gas
phase.
• When the anion formed is very stable (F-, Cl-) the negative value of E EA is large.
• Along the period the general tendency is an increase in the stability of the anion
formed, i.e. - EEA more negative.
• Down the groups, the general tendency is an increase in the stability of the anion
formed, i.e. - EEA more negative also.
2.5.3.4. Ion formation and size
• Elements in groups 1,2 and 13 of the main group tend to lose electron(s), forming
cations. Cations have a smaller radius than that of the neutral atom, because they
have fewer electrons but identical nucleic charge.
• Elements in groups 15 to 17 of the main group tend to gain electron(s), forming
anions. Anions have a larger radius than that of the neutral atom - because they have
more electrons but identical nuclear charge.

49
2.5.3.5. Electronegativity (χ).

Electronegativity is the ability of an atom in a molecule to attract bonding electrons.
It is measured on Pauli scale (χfrom 0.7 to 4.0).
When two atoms of different electronegativity form a chemical bond, the bonding electrons
will not be equally shared between the two atoms.
The more electronegative atom will attract the bonding electrons more - resulting in a partial
negative charge for the more electronegative atom and a partial positive charge for the less
electronegative atom.
Example. The water molecule:

δ-
O: 3.5
O
δ+
δ+
H H
H: 2.1
Partial charges Electronegativity
In the water molecule - the oxygen atom being more electronegative than hydrogen, attracts
the bonding electrons of the O-H bond - resulting in a partial negative charge for the oxygen
atom and a partial positive charge for the hydrogen atoms.

50

TOPIC 3. Molecular Shape and Chemical Bonding 51
Topic 3
Molecular Shape and Chemical

Bonding
Content
3.1. COVALENT BONDING......................................................................................... 52
3.1.1. The octet rule .......................................................................................... 53
3.1.2. Valency ................................................................................................... 53
3.1.3. Co-ordinate covalent bonds .................................................................... 54
3.1.4. Multiple bonds ......................................................................................... 54
3.1.5. Bond polarity ........................................................................................... 55
3.2. LEWIS STRUCTURE OF MOLECULES ................................................................... 56
3.2.1. Charged and delocalized species ........................................................... 56
3.2.2. Exceptions to octet rule ........................................................................... 58
3.2.3. Bridging atoms ........................................................................................ 60
3.2.4. Bond order, bond length and bond energy .............................................. 61
3.3. MOLECULAR SHAPE .......................................................................................... 64
3.3.1. Geometry and shape ............................................................................... 64
3.3.2. VSEPR .................................................................................................... 65
3.3.3. Further examples of Lewis structure / VSEPR ........................................ 71
3.3.4. Inert pair effects ...................................................................................... 73
3.3.5. Shape and Molecular Dipoles ................................................................. 75
3.4. VALENCE BOND (VB) THEORY ........................................................................... 77
3.4.1. Basis ....................................................................................................... 77
3.4.2. Hybrid Orbitals ........................................................................................ 78
3.4.3. VB construction ....................................................................................... 80
3.5. MOLECULAR ORBITAL (MO) THEORY- A BRIEF INTRODUCTION .............................. 82
Learning objectives
Basic Concepts of Chemical Bonding – chemical formulae ; ionic bonding ; covalent bonding
– octet rule, valency, bond polarity, Lewis structures, resonance, hypervalency, bond order,
length and dissociation energy ; molecular geometry – VSEPR Theory ; dipole moments ;
valence bond theory – hybrid orbitals ; molecular orbital theory.

3.1. Covalent Bonding

A covalent bond is a chemical bond that involves the sharing of an electron pair between
neighbouring atoms.
• Covalent bonding is energetically favoured. The bond energy is defined as the
energy that must be supplied to separate the bonded atoms to infinity.
• The bond length is the distance between the two nuclei; it is the internuclear distance
for which the bond energy is minimal.
Covalent bonds are affected by the electronegativity of the connected atoms.

• For two atoms with equal electronegativity, the covalent bond is non-polar.
E.g.: The hydrogen molecule: H-H; bond energy = 435 KJ mol-1; bond distance = 74 pm
1 e- 2 e-
H H
H H H
Figure. Non-polar covalent bonding formed by the interaction of two shared bonding
electrons.
• In a heteroatomic bond, the more electronegative atom tends to attract the electron
pair of the bond. The covalent bond is polar with a negative partial charge over the
more electronegative atom and a positive partial charge over the less
electronegative.
Example: The hydrochloride molecule: H-Cl
unpaired electron
lone pair bonding pair
e-
1 δ+ δ-
1+
δ+ δ-
H Cl
H Cl
δ+ δ-
H Cl
Figure. Polar covalent bonding formed by the interaction of two shared bonding
electrons. The bonding pair is not shared equally but is more attracted by the more
electronegative atom (here Cl) which polarises the bond.

3.1.1. The octet rule

• The octet rule states that atoms tend to be more stable when their electronic
configuration is similar to that of a noble gas. As a result, atoms tend to gain, lose or
share electrons so that their outer shell is populated by 8 electrons. (8 = octet).
• This rule applies to the main group elements of low atomic number (<20), including
carbon, nitrogen, oxygen, halogens, sodium, potassium, magnesium. The number 8
correspond to a full n-shell: 2 electrons in ns-orbital plus 6 electrons in np-orbitals.
• On ammonia (NH 3 ) the nitrogen (which has 5 valence electrons) is bond to three
hydrogen atoms: each hydrogen brings one electron to the molecule - so the total
number of electron in the nitrogen's outer shell is 8 (5(N) + 3(H)).
• On water molecule, the oxygen (6 valence electrons) is bond to two hydrogens. Each
hydrogen brings one electron to the oxygen's outershell, which is then populated by 8
electrons. (6(O) + 2(H))
3.1.2. Valency
The valency or valence number of an atom is the number of chemical bonds that an atom
may form to satisfy the octet rule. It is equal to the number of unpaired electron (upe). The
lone pair electrons are not counted as bonding, therefore the valency is the number of
valence electrons, less the lone pair electrons (lp).
The valency of an atom in a molecule is equal to the number of bond to the atom (single
bond count as one bond, double bond two and triple bond three).
Example:
• Nitrogen, has 5 valence electrons. Two of them are organised in one lone pair and
three are available for bonding: the valency is 3.
lp
upe N upe
upe
Nitrogen has one lone pair (lp) and three unpaired electrons (upe)
• Chlorine, has 7 valence electrons. Six electrons are organised in three lone pairs
and one electron is available for bonding: the valency is 1.
lp
lp Cl upe
lp
Chlorine has three lone pairs (lp) and one unpaired electron (upe)

3.1.3. Co-ordinate covalent bonds

This is also known as a dipolar bond; a dative covalent bond or a co-ordinate bond and
is a covalent bond in which the two electrons of the bond are provided by the same atom.
Example: Adduct of ammonia and boron trifluoride. The two electrons of the B-N bond are
provided by the nitrogen: as a result a positive charge appears on the nitrogen and a
negative charge on the boron.
Ground state Boron: [He] 2s22p1

eo lp
empty orbital (eo) H N H
F B F
upe B upe F H
upe
Boron trifluoride ammonia
empty orbital
F H F H
F B N H F B N H
F H F H
Excited state Boron: [He] 2s12p2 Adduct of ammonia and boron trifluoride
3.1.4. Multiple bonds
A double bond is a chemical bond involving four bonding electrons shared between two
atoms.
Example: Ethylene C 2 H 4 . Each carbon is surrounded by 8 valence electrons. The bonding
between the two carbons involves four valence electrons making a double bond.
H H H H
C C C C
H H H H
Figure. Double bond of ethylene.
A triple bond involves six bonding electrons shared by two atoms.

Example: Acetylene C 2 H 2 . Each carbon is surrounded by 8 valence electrons. The bonding
between the two carbons involves six valence electrons: a triple bond.
H C C H H C C H
Figure. Triple bond of acetylene.

The valency of carbon is 4 in ethylene and acetylene:

• In ethylene, each carbon has four bonds: two single bonds with hydrogen plus one
double bond with carbon.
• In acetylene, each carbon has four bonds: one single bond with hydrogen plus one
triple bond with carbon.
3.1.5. Bond polarity

When one of the two atoms involved in a covalent bond attracts the bonding electron pair
more than the other atom, partial charges appear and the bond is polar. A negative partial
charge (δ-) appears over the atom attracting the electronic density and a positive partial
charge (δ+) appears over the other one.
The ability to attract the electronic density is evaluated using the empirical value of
electronegativity χ. The higher the value the greater the pull on electrons and the higher the
difference in electronegativity between the two atoms bonded the higher the polarity.
The polarity scale spreads continuously from non polar (the two atoms share the electron
density equally -have equal χ) to ionic (one atom takes the totality of the electron density
leaving nothing to the other atom - the difference in χ between the two atoms is well over
0.5). Between these two extremes the covalent bond is essentially non polar (difference less
than 0.5) or polar (difference over 0.5).
The polarity of a bond is measured by the values of the partial charge (δ+ and δ-) created.
µ is the dipole moment measured in Debye (D)

( 1D = 3.336 x 10-30 Cm)
µ = q x e x r (C m) q is the partial charge on the atoms
e is the charge of an electron in C (coulomb)
r is the bond length in m (metre)
Example. HF has a dipole moment of 1.83 D and a bond length of 92 pm (92x10-12m)

Calculate the value of q
q = µ / (e x r) = 0.41

3.2. Lewis Structure of Molecules

Lewis electron dot diagrams show the valence electrons arround the atoms of a molecule
and identify their nature as lone pair (lp), bonding pair (bp) or unpaired electrons (upe).
The molecular shape is dictated by the position of the electrons around the central atoms.
Building the Lewis structure of molecules in 5 steps: Methanol, CH 3 OH
1. Start from the molecular formula. Determine for each atom the total number of
valence electrons. When dealing with an anion, add one electron per charge. For a
cation, remove one electron per charge.
2. Place the element of lowest valence around the element of highest valence. Then
assign the bonds (single double or triple) to satisfy the valency of the atoms of lowest
valency.
3. Calculate the number of valence electrons around the central atom, adding the
shared electrons from the peripheral atoms.
4. Assign the shared electrons to bond pairs (bp).
5. Assign the residual valence electrons to lone pairs (lp).
3.2.1. Charged and delocalized species

• To draw the Lewis structure of negatively charged species, the general method of
construction is followed, adding one extra valence electron per negative charge.
Example. Tetrahydroborate ion: BH 4 -.
eo
H H H H
B H H
H B H H B H
Boron Electron Four hydrogens
H H
Tetrahydroborate
Note: Boron is surrounded by 8 electrons. The octet rule is satisfied.
• The Lewis structure of positively charged species is constructed following the general
method, removing one valence electron per positive charge.

Example. Ammonium ion: NH 4 +.

H H
H H
H N H H N H
N H H
H H
Nitrogen Four hydrogens, of which
one had its electron Ammonium ion
removed (proton with
positive charge)
Note: Nitrogen is surrounded by 8 electrons. The octet rule is satisfied.
• When dealing with delocalised bonding: more than one Lewis structure can be
drawn. This happen when a bond pair does not have a definite position between two
atoms only but over three or more atoms. Each possible Lewis structure is called a
resonance structure; the molecular skeleton does not change but the arrangements
of the electrons change.
Example. Nitrate: [NO 3 ]-. Three equivalent Lewis structures (resonance structures)
are possible, because one bond pair is delocalized over four atoms. The nitrogen is
positively charged and two negative charges are delocalized between the three
oxygens. Each oxygen has a charge of -2/3.
N O O O
Nitrogen Three oxygens One electron
O O O
N O N O N O
O O O
-2/3
O O O O
N O N O N O or N O -2/3
O O O O
-2/3
Nitrate ion: three equivalent Lewis structure are possible
Note. The phenomenon of resonance is symbolized by double arrow between the resonance
structures.

3.2.2. Exceptions to octet rule

• Hypervalence. (more than 8 valence electrons)
A hypervalent molecule contains one or more main group elements formally bearing more
than eight electrons in their valence shells.
It can happen when:
o The central atom is a main group element with a valence shell n ≥ 3. *
o Central atom must use more than 4 valence orbitals,
o Peripheral atoms have large χ (O, F, Cl, …)
Example of hypervalent molecules: Phosphorus pentafluoride (PF 5 ), sulfur hexafluoride

(SF 6 ), SF 4 ,Chlorine trifluoride (CIF 3 ), Triiodite (I 3 -), SOCl 2 , XeOF 4 , … ClF 5 , XeF 6
(*) Note. The central atom must use more than 4 valence orbitals, so hypervalence is
naturally limited to valence shell, n ≥ 3.
upe
F [He] 2s2 2p5
s p d
2 3 0
Ground state P [Ne] 3s 3p 3d
s p d
P in PF5 [Ne] 3s2 3p3 3d0
F P F
F F

Figure. Hypervalent phosphorus pentafluoride (PF 5 ). The phosphorus undergoes excitation

to promote one electron from 3s orbital to one empty 3d orbital, providing five unpaired
electrons and allowing the formation of PF 5 molecule.
5s 5p
5d
I [Kr] 4d105s2 5p5
5s 5p
5d
10 2 6
ground state of I-[Kr] 4d 5s 5p
5s 5p
5d
- -
I in I3 [Kr] 4d105s2 5p5 5d1
Lewis structure of triiodide I I I
Figure. Hypervalent triiodide (I 3 -). The central atom is ion iodide; its extra electron is
promoted to the empty 5d orbital – allowing the formation of two single bounds. The central
atom has therefore three lone pairs.
• Less than 8 valence electrons. The case of boron trifluoride.
Looking at the atomic orbitals, the central atom of boron trifluoride has only 6 valence
electrons, hence does not follow the octet rule.
2s 2p
2 1
B [He] 2s 2p F
2p B
2s
F F
1 2
B in BF3 [He] 2s 2p
Lewis structure of BF3

However, three resonance structures can be drawn in which one fluoride, already bonded to
the boron by a single bond, provides co-ordinate pi-bond to the central atom’s empty p-
orbital. In these three resonance structures, the octet rule is respected (but fluorine has to
bear a positive charge).
F F F
B B B
F F F F F F
Resonance structures of BF3
Which Lewis structure best describe BF 3 ?

• If several Lewis structure are possible; choose the one with the lowest charges
• The zwitterion description shows a positive charge on fluorine (not best).
3.2.3. Bridging atoms

Bridging chloride.
If boron is stable with 6 valence electrons as in BF 3 , aluminium although in the same group
is not so stable in AlCl 3 .
2 1
Al [Ne] 3s 3p
Cl
high temperature, gas phase Al Cl
Cl
lower temperature, gas phase and liquid phase
Cl
Cl
Cl Cl Cl Cl
Al Al Al Al
Cl Cl
Cl Cl
Cl Cl
At lower temperatures dimers form via Cl bridging using Cl lone pairs and the Al empty p-
orbital, forming a co-ordinate covalent bond (2 centers and 2 electrons).
Note. In the solid phase, the structure is polymeric

Bridging hydrogen.
Borane, BH 3 dimerises to form diborane B 2 H 6 . Here the bridge uses bond pair: the electron
pair from BH bond is shared to make a second BH bond: 3 center 2 electrons bond.
21
B [He] 2s 2p
H H H H
H H H H H H
2 B H B B B B B B
H H H H H H
H H H H
3.2.4. Bond order, bond length and bond energy

• Bond order (bo) is the number of chemical bonds between two atoms.
Example:
The bond order in diatomic nitrogen (N≡N) is 3
The bond order in hydrogen chloride (H-Cl) is 1.
• Covalent radius is half the internuclear distance (the bond length) in homonuclear
bond and is bond order specific.
Example:
Molecules Bond length Covalent radius
H3C CH3 154 pm 77 pm
H2C CH2 134 pm 67 pm
HC CH 120 pm 60 pm
• Bond length (bl) between two atoms is the addition of their covalent radii.
Example:
Molecules Bond length Covalent radius
Cl Cl 198 pm Clcr = 99 pm
H3C CH3 154 pm Ccr = 77 pm
H3C Cl 178 pm
Clcr + Ccr = 176 pm

• Bond energy (be) is directly correlated with bond order (bo) and inversely correlated
with bond length (bl).
Example:
Molecules Bond order Bond length Bond energy (kJ.mol-1)
H3C CH3 1 154 pm 346
H2C CH2 2 134 pm 598
HC CH 3 120 pm 813
• Bond energy is always positive: it is the energy required to break up the bond. When
a bond is made, energy is released (exothermic).
•
Single Bonds
H C N O S F Cl Br I
H 435
C 416 346
N 391 285 159
O 464 359 201 146
S 366 272 266
F 570 485 272 190 326 159
Cl 432 327 193 218 255 247 242
Br 366 285 201 217 249 216 193
I 298 213 201 278 208 175 151
Multiple Bonds
C=C 598 C=N 615 C=O 806
C≡C 813 C≡N 866 C≡O 1072
N=N 400 N=O 607 S=O (in SO2) 532
N≡N 945 O=O 498 S=O (in SO3) 469
P≡P 490 S=S 425 Si=O 642
Table of single and double bonds energy (in kJ.mol-1).

Exercise 1: Calculate the heat of reaction ∆H (ie enthalpie change) for the reaction:
C2H2 + 2H2 C2H6
H H
H H
H C C H H C C H
H H
H H
Bond broken be total bond made energy released total
1 C C 813 813 1 C C -346 -346
2 H H 2 X 435 870 4 C H 4 X -416 -1664
1683 kJ - 2010 kJ
∆H = 1683 -2010 = -327 kJ
Exercise 2: Calculate the heat of reaction (∆H) for the formation of sulfur bromide (S 2 Br 2 )
from the elements in their standard states and comment on its sign.
S8 + 4 Br2 4 S2Br2
S S
Br
S S
4 Br Br 4 S S
S S
Br
S S
Bond broken be total bond made energy released total
4x S S 4 x 266 1064 8 x Br S 8 x - 217 - 1736
4 x Br Br 4 x 193 772
1836 kJ - 1736 kJ
∆H = 1836 -1736 = + 100 kJ (ie reaction is endothermic)

3.3. Molecular Shape

The molecular shape is determined experimentally:
• By electron diffraction in gas phase
• By X-ray diffraction in crystalline phase
The molecular shape can be predicted from the Lewis structure of the molecule, using the
VSEPR theory (Valence Shell Electron Pair Repulsion). Valence electron pairs form groups
and are arranged around the central atom and repel each other. Therefore the shape of the
molecule depends primarily on the number of groups.
Example: the molecular shapes of boron trichloride and nitrogen trichloride.
lp
Cl Cl
N N
B B Cl Cl
Cl Cl
Cl Cl Cl Cl Cl Cl
BCl3: planar shape NCl3: non-planar shape
The shape of a molecule is determined by the three-dimensional arrangement of the valence

electrons; whether in bonding pairs, in lone pairs or unpaired.
3.3.1. Geometry and shape

The shape of a molecule is the disposition of all the molecule’s atoms. It is determined by
the arrangement of the bond pairs (bp) around central atoms.
The geometry of a molecule is the three-dimensional arrangement of the molecule’s valence

electrons (bond pairs, lone pairs and unpaired electrons). The molecular geometry
determines many of the substance’s properties such as chemical reactivity, polarity, colour
or magnetism.

Examples: sulfur hexafluoride (SF 6 ), chlorine pentafluoride (ClF 5 ), xenon tetrafluoride

(XeF 4 ).
SF6 ClF5 XeF4
F F F
F F F F
S Cl F Xe F
F F F F
F F
Shape octahedral square pyramidal square planar
F F
F F F F F F
S Cl Xe
F F F F F F
F
Geometry octahedral octahedral octahedral
3.3.2. VSEPR
The Valence Shell Electron Pair Repulsion (VSEPR) theory is used to predict the shape of
molecules and is based on electron-pair electrostatic repulsion. The model is based on a
central atom A and a number of valence electron group (electron-pairs) which can be
bonding (X) to a substituent or non-bonding (lone pair) (E). All valence electrons groups
repel each other and dictate the shape of the molecule.
The basic geometry.

For simple molecules, made of a central atom A and where all electron-pairs X are bonding
to substituent(s) we describe five basic geometries depending on the number of valence
electron group X (from 2 to 6X).
Example:
2X 3X 4X 5X 6X
X X o X X X
120 109
o
X 90o X X
108o
A A X A A X A 90o
X
X X X 120o X X
X
X X X
linear trigonal planar tetrahedral trigonal bipyramidal octahedral

Predicting molecular shape with VSEPR theory.
• Determine the basic geometry from the Lewis structure.

• Lone pairs have greater electrostatic repulsion than bonding pairs, therefore they
require more space than bonding pairs. When they are present; refine the geometry
and determine the molecular shape.
Examples: with one lone pair AXnE.
1 lp 1 lp 1 lp 1 lp
AX2E AX3E AX4E AX5E
X <90o X
<120o X X
X
A A o A A
X X <120
X X X X
X o
<109 X X <90o
bent or angular trigonal pyramid see-saw square pyramidal
Example: with two lone pairs AXnE 2 .
2 lp 2 lp 2 lp
AX2E2 AX3E2 AX4E2
<90o X
X X X
X A A A 90o
o X X
<<109 X
X
bent or angular T-shape square planar

Example: with three lone pairs AXnE 3 .
3 lp 3 lp
AX2E3 AX3E3
X
180o X X
A A <90o
X
X
linear T-shape
The VSEPR theory in four simple rules:
• rule 1. The distances between valence electron groups X are maximized

• rule 2. Lone pairs (lp) require more space than bonding pairs (bp).
• rule 3. Multiple bonds require more space than single bonds
• rule 4. The space required by bp decreases with increasing χ of peripheral atom.
The rules 1 and 2 give the basic shape of the molecule and rules 3 and 4 refine the shape.
Rule 1: The distances between valence electron groups X are maximized
- Two groups (AX 2 ): linear geometry.

Note: a multiple bond counts as one group.
180o
F Be F 2 bp, 2 single bonds AX2 F Be F Linear shape

o
180
O C O 4 bp, 2 double bonds AX2 O C O Linear shape

o
180
H C N 4 bp, 1 triple bond AX2 H C N Linear shape

and 1 single bond

- Three groups (AX 3 ): trigonal geometry.

Note: a lone pair E counts as one group.
F
F o
120
F B F 3 bp, 3 single bonds AX3 B trigonal planar
F F
geometry
(trigonal planar shape)
O
S O 5 bp, 2 double bonds AX2E S trigonal planar
and 1 lone pair O geometry
O
(angular shape)
- Four groups (AX 4 ): tetrahedral geometry.
H H
109.5o
H C H 4 bp, 4 single bonds AX4 tetrahedral
H C
H H
H
H N H 4 bp, 3 single bonds AX3E tetrahedral geometry

H N
H H
H
(trigonal pyramidal shape)
O H 4 bp, 2 single bonds AX2E2 tetrahedral geometry

H O
H
H
(bent or angular shape)
-Five groups (AX 5 ): trigonal bipyramidal (tbp) geometry.
F F
o
F 90
F 5 bp, 5 single bonds AX5 F
P P F trigonal bipyramidal
F F F
F
F F
F AX4E
S 5 bp, 4 single bonds F trigonal bipyramidal
S
and 1 lone pair
F F F
F
(see-saw shape)

-Six groups (AX 6 ): octahedral geometry.

F F
F F
P 6 bp, 6 single bonds AX6 F F octahedral geometry
P
F F F F
F F
F
F
I 6 bp, 5 single bonds AX5E F F octahedral geometry
I
and 1 lone pair
F F F F
F F
(square pyramidal shape)
O
F
7 bp, 4 single bonds, AX5E F F octahedral geometry
Xe Xe
1 double bond, and
F F F
F 1 lone pair
F O
(square pyramidal shape)
Rule 2: Lone pairs (E) require more space than bonding pairs (X).
The electrostatic repulsion caused by lone pairs is greater than the repulsion caused by
bonding pairs.
This has an effect on the molecule’s angles (the lone pair(s) push the bonding pairs away).
H C H N O
H H H H H H
109.5o 107o 105o
And has an effect on molecular shape (lone pairs have more space in equatorial position
than in axial):
F
F
S
F XS F
F F
F F
(see-saw shape) (trigonal pyramidal shape)
prefered isomer: lp equatorial lp axial is not favourable

F F F
equatorial to o F F
equatorial angle 102 S Cl Xe
F
F F F
o
axial to axial angle 173
lone pairs in equatorial position
Rule 3: Multiple bonds require more space than single bonds.

A double bond is made of four valence electrons, a triple bond of six; they have a greater
electrostatic repulsion than a bond pair.
H H
F O C
B C C
F F H H H H
o o o
120 116 117
Rule 4: The space required by bp decreases with increasing χ of peripheral atom.

The bonding pairs are attracted by the more electronegative atom. The more electronegative
the peripheral atom the greater the attraction toward the periphery and less space is
required by the bonding pair around the central atom.
O O
δ+
H H δ- F F δ-
electronic density is between C and H electronic density attracted by F

more space available around the central atom
O O
H H F F
o o
116 108
The rules 1 and 2 give the basic shape of the molecule and rules 3 and 4 refine the shape.

When the peripheral atoms are different the refined shapes is inevitably a distorted basic
shapes.
Example of sulfur hexafluoride (SF 6 ) and sulfur monochloride pentafluoride (SClF 5 ).

Chloride is less electronegative than fluoride, therefore requires more space.
90o F 90o Cl >90o

F F F F
S S
F F F F
F F
no distorsion Cl is less χ than F
each angle is 90o
Cl requires more space than F
each angle is 90o
distorsion
octahedral octahedral distorted octahedral
3.3.3. Further examples of Lewis structure / VSEPR
Chlorine dioxide (ClO 2 +)
• First; write the Lewis structure.
6 e per O plus 7 e on Cl
each O needs 8 valence electrons O Cl O
remove one electron to make positive charge O Cl O
Lewis structure O Cl O
• Then apply the VSEPR rules; count the number of groups and apply rules 1 to 4 to
determine and refine the molecular shape.
3 groups of valence electron-pairs gives a basic trigonal planar geometry. 2 groups

are double bond Cl=O and 1 is a lone pair. AX 2 E
Cl
O O
bent shape
trigonal planar geometry
The molecule has a bent or angular shape and a trigonal planar geometry.
Azide ion (N 3 -)

one lone pair from central N is used to make a co-ordinate covalent bond
lp
5 e per N
N N N
each N needs 8 valence electrons

N N N
add one electron to make negative charge
Lewis structure N N N
2 groups of valence electron-pairs, Linear geometry. AX 2.
N N N
The molecule has a linear shape and a linear geometry.
Note: the charges on the nitrogens; the central atom forms a co-ordinate covalent bond with
one peripheral nitrogen atom and therefore gets a positive charge (for the same reason the
peripheral nitrogen gets a negative charge). The electron is added to the second peripheral
nitrogen which comes with a negative charge.

Nitric acid (HNO 3 )
H
5 valence electrons on N, 1 on H and 6 per O
lone pair of N forms a co-ordinate bond with one O O N O
H H O
Lewis structures: O N O O N O
O
O
3 groups of valence electron-pairs, Trigonal planar geometry. AX 3.
1 group is a single bonding pair (N-O) and 2 groups are partial double bond (the
structure is delocalized). These two groups require more space than the first one:
therefore the molecule has a distorted trigonal planar shape.
-1/2
O
HO N
O -1/2
3.3.4. Inert pair effects

The inert pair effect is a tendency of the s valence electrons to remain as a lone pair in
compounds of post-transition metals.
Selenium hexachloride (SeCl 6 2-)
s p d
2 4
Se [Ar] 4s 4p
s p d
Ground state Se2- [Ar] 4s2 4p6
s p d
Excited state Se2- [Ar] 4s2 4p3 4d3
We expect the 8 valence electrons to form seven valence electron groups: six bonding pairs
with Cl and one lone pair; a AX 6 E geometry (pentagonal bipyramidal geometry).

pentagonal bipyramidal
We do not obverse a AX 6 E geometry but a AX 6 octahedral geometry.
2
Cl
Cl Cl
Se
Cl Cl
Cl
octahedral geometry
The valence electrons of the 4s-orbital are inert, they do not affect the shape of the
molecule: they are stereochemically inactive.
For post-transition elements, such as Se, the valence s-electrons are relatively deeply buried
and are not really valence. So if s-electrons are not part of the valence, only 12 valence
electrons are involved in forming six groups and we observe a AX 6 octahedral geometry.
Note. This is related to the tendency of post-transition elements to form two oxidation states:
a normal oxidation state (using all valence s- and p-electrons and a lower oxidation state
(leaving the s-electrons).
This phenomenon is known as the thermodynamic inert pair effect.

Example:
Tin Sn Sn (IV) Sn (II)
[Kr] 4d
10
5s 5p
2 2
[Kr] 4d10 [Kr] 4d10 5s2
Lead Pb Pb (IV) Pb (II)

14
5d10 6s2 6p2
14 10 14 10 2
[Xe] 4f [Xe] 4f 5d [Xe] 4f 5d 6s
Indium In In (III) In (I)

10 2 1 10 10 2
[Kr] 4d 5s 5p [Kr] 4d [Kr] 4d 5s
Thallium Tl Tl (III) Tl (I)

14 10 2 1
[Xe] 4f 5d 6s 6p [Xe] 4f14 5d10 [Xe] 4f
14
5d
10
6s
2
3.3.5. Shape and Molecular Dipoles

The shape of molecule has an effect on the molecular magnetism. When two bonded atoms
have different electronegativity χ the bond is polarized. In molecules where there is more
than one polarized bond; the dipoles resulting from polar bonds can either cancel each other
(and the molecule is not polar) or contribute to create a molecular dipole and the molecule is
polar, depending on the shape of the molecule.
Bond dipole moment µ (expressed in Debye) is used to measure the polarity of a chemical
bond, where d is the bond length and δ the value of the partial charge.
µ=δd
• It is a vector, parallel to the bond axis.

• It is pointing from negative to positive charge.
• In polyatomic molecules the total molecular dipole moment is the vector sum of
individual bond dipole moment and is depending on the molecular shape.
The measure of the molecular dipole gives information on molecular shape.

Example: The molecular dipole moment of water H 2 O is 1.85 Debye, of carbon dioxide is 0
Debye.
δ-
O net dipole = 1.85 D molecule is bent
H H
δ+ δ+
δ+
δ- O C O δ- net dipole = 0 D molecule is linear
Example 2 : Two isomers of 1,2-Dichloroethylene are isolated, one (a) is polar with a
molecular dipole moment of 1.90 D and the second (b) is non-polar with a molecular dipole
moment of 0 D. Determine which is the cis and trans-isomers from the value of the
molecular dipole moment.
δ- δ-
Cl Cl
δ+ δ+ net dipole = 1.90 D (a) is cis-isomer
C C
H H
δ-
Cl H
δ+ δ+ net dipole = 0 D (b) is trans-isomer
C C
H Cl
δ-

3.4. Valence Bond (VB) Theory

The valence bond (VB) theory is a complement to the molecular orbital (MO) theory and was
developed to explain chemical bonding.
• It focuses on localized bonding (when MO theory describes orbitals covering the

whole molecule).
• Is not suited to describing delocalization.
• Is a good qualitative model
3.4.1. Basis
According to the theory, a covalent bond is formed between two atoms by the overlap of two
atomic orbitals of the same phase. Each atomic orbital containing one unpaired electron.
Example. Two s-orbitals of the same phase form the single bond in H 2 .
AO AO orbital overlap
H (1s) H (1s) H2 (Sigma s)
Example. One s-orbital from H and one p-orbital from Cl form HCl single bond.
AO orbital overlap
AO
Cl (3p) HCl (Sigma sp)
H (1s)
Note. The electrons have opposite spin in the overlapped orbital.

3.4.2. Hybrid Orbitals
Atomic hybrid orbitals are the result of mixing atomic orbitals (s, p, d, etc) from the same
atom and have their own shape and energy. Hybrid orbitals are very useful in explaining
molecular geometry and bonding properties.
Example. Methane CH 4 is a tetrahedral molecule in which each bond is similar and identical
in energy.
Looking at the atomic orbital of carbon:
Ground state of C [He] 2s2 2p2 Energy
2s 2p 2p
2s
In order to create four bonding pairs, one electron from the 2s-orbital is promoted to an
empty 2p orbital. The result is an excited state where all four valence electrons (upe) from C
are available for bonding with the upe of the four hydrogen atom.
Excited state of C [He] 2s1 2p3 Energy
2s 2p 2p
2s
In the excited state, four upe are available for bonding, but are from two different energy
levels. To reflect the fact that all bonds formed are of identical energy one s-orbital is mixed
with all three p-orbitals resulting in four hybrid sp3 orbitals (of identical energy level).
sp3 hybridisation Energy
sp3
3
sp

The shape of the hybrid sp3 atomic orbitals

• One s-AO is mixed with three p-AO
• Each of the four hybrid sp3 orbitals retains 25% of the s-AO character and 75 % of
the p-AO.
• The energy level of the new hybrid orbitals is intermediate, between the s and p AO’s
energy levels.
25% 75%
s p sp3
Bonding hybrid orbital:
Four covalent bonds are formed between the four sp3 hybrid orbitals of carbon and by the
overlap of four s-atomic orbitals of the four hydrogen atoms making four sigma (σ) bonds.
C+4H CH4
3
The hybridization reflects the geometry; sp hybridisation of the central carbon is consistent
with the observed tetrahedral geometry on CH 4 .
For other geometries, other hybridisation schemes are used.

Example:
H H H
sp 3
2 sp
H C C H C C sp C
H
H
H H H
linear trigonal tetrahedral
F F
3
F dsp F F
P F S 2
d sp
3
F F F
F F
trigonal bipyramidal octahedral
Valence bond theory allows a simple view of chemical bonding once the geometry is known.

3.4.3. VB construction
To construct the valence bonds, first the Lewis structure and then the geometry (using
VSEPR) must be determined.
Example. BF 3
2 1 2
B [He] 2s 2p sp hybridised B
F
2p 2p F
2 F
sp
2s
2
two p-orbitals are mixed with s-orbitals, making three sp hybrids
one p-orbital is not hybridised and is perpendicular to the molecular plane
Example. H 2 O
AO
O [He] 2s2 2p4 3
sp hybridised O
lp lp
2p
H
3
sp H
2s
three p-orbitals are mixed with s-orbital, making four sp3 hybrids.
two sp3 orbitals overlap a H (1s) orbital and two are lone pairs.

Example. SF 6
F
F F
AO
F F
S [Ne] 3s2 3p4 d2sp3 hybridised S F
3d 3d
3p
d2sp3
3s 2 3
six d sp orbitals result from mixing two d threep and one s AO.
Example : C 2 H 4 . Representation of multiple-bonds with VB theory

Three sp2 orbitals result from mixing one s and two p-orbitals. These three new orbitals
overlap with two hydrogen (1s) orbital and one (sp2) orbital from the second carbon; forming
three single bonds (sigma bonds).
2 2 2
ground state of C [He] 2s 2p hybridisation sp
p p
Energy
H H
C C
H H
2p p
sp2
2s
The sp2 hybridisation leaves one p-orbital unchanged on each carbon. Each p-orbitals are
perpendicular to the molecular plan and parallels to each other: they overlap and form a π
bond.
2
hybridisation sp + p
π bond
H H
C C
H H
p
sp2
A double bond is made of one sigma (σ) bond and one pi (π) bond.
Note. The π bond has two opposite phases, one above and one bellow the molecular plan.

3.5. Molecular Orbital (MO) Theory- a brief introduction

The molecular orbital theory is a method for determining molecular structures in which
electrons are not assigned to individual bonds between atoms, but are delocalised on the
whole molecule.
Atomic orbitals have phase (+ or -).
• Bonding molecular orbitals (BMO) are formed when two AO of the same phase
combine, they are more stable than the two AO.
• Antibonding molecular orbitals (ABMO) are formed when two AO of opposite phase
combine, they are less stable than the two AO.
• In AMO, the electronic density between the two atoms is zero.
Molecule of H2, constructed from two H, called HA and HB

Energy
ABMO ψ A - ψ B
ψA ψB
BMO ψ A + ψ B
The bond order of a pi orbital is:
Bo = (number of electron pairs in BMO) – (number of ep in ABMO) = 1

83
TOPIC 4. CHEMISTRY OF THE ELEMENTS OF THE MAIN GROUP
Topic 4
Chemistry of the Elements of the

Main Group
Content
4.1. INTRODUCTION ........................................................................................................... 84
4.1.1 Natural abundance ............................................................................................ 84
4.1.2 Classification of Main Group elements................................................................ 85
4.1.3. Physical forms of the Main Group Elements ...................................................... 85
4.1.4. Properties of the Main Group compounds ......................................................... 88
4.3 CHEMISTRY OF HYDROGEN H ...................................................................................... 90
4.3.1. Properties .......................................................................................................... 90
4.3.2. Compounds of Hydrogens ................................................................................. 91
4.3.3. Hydrogenation reactions .................................................................................... 93
4.3.4. Production of Hydrogen ..................................................................................... 94
4.3.5. Industrial uses of Hydrogen ............................................................................... 95
4.3.6. Reactions of Main Group Hydrides .................................................................... 96
4.3.7 . Hydrogen Bonding ............................................................................................ 97
4.4. CHEMISTRY OF THE HALOGENS (GROUP 17) ................................................................ 98
4.4.1. Properties .......................................................................................................... 98
4.4.2. Production of Halogens ..................................................................................... 98
4.4.3. Industrial use of Halogens ................................................................................. 99
4.4.4. Common stoichiometries of the Halides of period 2 and 3 ............................... 100
4.4.5. Hydrogen halides............................................................................................. 102
4.4.6. Halogen oxyacids ............................................................................................ 102
4.4.7. Interhalogen Fluorides ..................................................................................... 103
4.5. CHEMISTRY OF THE CHALCOGENS (GROUP 16: O, S, SE) ........................................... 104
4.5.1. Production ....................................................................................................... 104
4.5.2. Stoichiometry of most common oxides of period 2 and 3 ................................. 104
4.5.3. Reactivity of Alkali metals with O 2 , H 2 O,.......................................................... 104
4.5.4. Oxides of group 14 (C, Si) ............................................................................... 105
4.5.5. Oxides of group 15 (N, P, As) .......................................................................... 107
4.5.6. Oxides of Sulfur ............................................................................................... 109
4.6. ENVIRONMENTAL IMPACT OF MAIN GROUP COMPOUNDS ............................................ 110
4.6.1. Acid rain .......................................................................................................... 110
4.6.2. Ozone depletion .............................................................................................. 111
4.6.3. Greenhouse Effect........................................................................................... 113
Prerequisite knowledge
Covalent bonding; octet rule; VSEPR; electronegativity; hypervalency; hybridization.
Learning objectives
Elemental abundance and physical form ; definition of main group elements ; valence orbital
availability ; properties of main group compounds.
Descriptive chemistry of hydrogen, the halogens, oxygen and sulfur.

84
4.1. Introduction
The main group elements include the s-block elements (group 1 and 2) and the p-block
elements (group 13 to 18).
H Electronegativity Table of the Main Group Elements He

2.1
G1 G2 G13 G14 G15 G16 G17 G18
Li Be B C N O F Ne
1.0 1.5 2.0 2.5 3.0 3.5 4.0
Na Mg Al Si P S Cl Ar
0.9 1.2 1.5 1.8 2.1 2.5 3.0
K Ca Ga Ge As Se Br Kr
0.8 1.0 1.6 1.8 2.0 2.4 2.8
Rb Sr In Sn Sb Te I Xe
0.8 1.0 1.7 1.8 1.9 2.1 2.5
Cs Ba
0.7 0.9
Metals χ<2
Metalloids χ~2
Non-Metals χ>2
These elements are the most abundant elements in the solar system and in the universe and
are also the major components of the human body.
4.1.1 Natural abundance

The six most abundant elements in the universe: H (for 91%), He, O, C, N, Ne, are all
main group elements.
The mass of earth is made principally of Fe (32%), O (30%), Si (15%), Mg (14%), S (3%),
Ni (1.8%), Ca (1.5%), Al (1.4%). All except for Fe and Ni, are main group elements.
The human body is composed principally of: O (65%), C (18%), H (10%), N (3%), Ca
(1.5%), P (1.2%), K (0.2%), S(0.2%), Cl (0.2%), Na (0.1%), Mg (0.05%), all these are main

85
group elements. The transition metal element: Fe, Co, Cu, Zn account for less than 0.05%
(and are called trace elements).
4.1.2 Classification of Main Group elements.

The main group elements are classified according to their conduction properties into three
groups: Metals, Metalloids and non-Metals
Non-metals are not electrical conductors, they are characterised by a high electronegativity
value (χ over 2). The valence electrons of non-metals are strongly attracted to their positively
charged nucleus and are not available to conduct electricity.
Metals are electrical conductors; they have a low electronegativity value (χ under 2). The
valence electrons of metals are more loosely attracted to the nucleus and are free to conduct
electricity. Metals make crystal lattice structures in which electrons can flow freely.
Metalloids or semi-metals show intermediate conduction properties (they are semi-

conductors). Their electronegativity values are close to 2. The valence electrons of
metalloids are localised around the nucleus but can also be moved (and therefore conduct
electricity) when excited by small inputs of energy. Semi-conductors elements such as Si,
As, Sb play an important part in microelectronic devices.
4.1.3. Physical forms of the Main Group Elements
S-BLOCK ELEMENTS, groups 1 and 2 (H excepted) are typically metallic and form lattice
structures.
Lattice structure. The most stable form for lithium metal at 298K is the body-centered cubic
(bcc) structure. Under standards conditions, all of the group 1 (alkali metals) elements have
a bcc structure (bcc is made of two interlocked cubic arrays of atoms).
304 pm
electron
lithium ion in lattice every Li is surrounded by eight other Li
The elements of the first two groups (such as alkali metals: Li, Na, K, and alkaline earth
metals: Be, Mg, Ca) are silver-coloured, soft, low-density metals. They have respectively one
and two valence electrons which are easily lost. They form lattice structures in which the
valence electrons are free to conduct electricity. The s-block elements are characterised by
low ionisation energies and hence are very reactive.

86
P-BLOCK ELEMENTS
Monoatomic structure (noble gases). The noble gases under standard conditions are all
odourless, colourless, monoatomic gases with very low chemical reactivity.
Diatomic structures can be gas, liquids or solids, depending on temperature. For example
hydrogen (H 2 ), nitrogen (N 2 ), oxygen (O 2 ), chlorine (Cl 2 ).
H H N N O O Cl Cl
Lewis structures of diatomic molecules: H 2 , N 2 , O 2 , Cl 2 .
Polyatomic structures
B, P, S, C have several molecular allotropes; discrete polyatomic molecules such as B 12 , P 4 ,
S 8 , C 60.
Boron has many molecular allotropes such as B 12 , B 28 , B 50 , B 105-108 , B 192 .
Alfa-Boron has a unit cell of twelve B atoms: B 12 . The structure is icosahedral. Each boron
(B: [He] 2s2 2p1) has three valence electrons, and the icosahedral structure is achieved by
three centers two electrons bridging. Each bridge is made of one electron pair from a B-B
bond and one empty orbital: a pair of electron is shared between three borons: this makes a
3 centre 2-electron bond. In B 12 structure, each boron atom is bonded to five others.
empty orbital
B
B B
B B B
B B
B B B
bp B B B
B B
3 centers 2 electrons bond

B 12 icosahedron.
Phosphorus can exist in several molecular allotropes such as P 2 , P 4 .
White phosphorus, tetraphosphorus P 4 is a molecule made up of four P atoms and has a

tetrahedral structure. Each phosphorus (P: [Ne] 3s2 3p3) has a sp3 hybridisation. In the P 4
structure, the four lone pairs are pointing outside the structure and six sigma bonds link the
four phosphorus atoms together.

87
lp
P P
P
tetraphosphorus molecule
Carbon is known for its two main allotropes: diamond and graphite and also for forming
carbon nanotubes and many other molecular allotropes such as fullerenes C 20 , C 60 , C 70.
In Fullerene C 60 , each carbon has sp2 hybridisation and is bonded to three neighboring
carbons. The ball shape of fullerene is achieved by a series of six and five carbon rings (just
like a football).
Fullerene, C 60 is made of 60 sp2 carbons organized in series of 5 and 6 member rings.
Extended lattice structure
G14 G15 G16

C
2.5
Si P S
1.8 2.1 2.5
Ge As Se
1.8 2.0 2.4
Sn Sb Te
1.8 1.9 2.1
Carbon exists in various structural forms and like some other main group elements (Si, P, S,
Ge, As, Se, Sn, Sb, Te, Bi) can make lattice structures (infinite networks) such as diamond

88
(3D structures of sp3 carbons made of sigma-bonds), graphite and nanotubes (2D structures
of sp2 carbons involving sigma and π-bondings).
2
3
sp sp
C C
Diamond structure
Graphite, Fullerene, nanotube structure
Note. Graphite is made of layers of extended lattices (principally flat molecular sheets of sp2
carbon made of six carbon rings).
Tin has few allotropes: α−, β−, γ− and σ−tin.
Alfa-tin (α-tin) or grey tin is a non metallic allotrope; it is brittle. It has a diamond cubic crystal
structure with covalently bonded atoms: the valence electrons in alfa-tin are not available for
conduction and the structure is brittle and non metallic.
Beta-tin (β-tin) or white tin is a metallic allotrope: it had a lattice structure which is stable and
malleable.
4.1.4. Properties of the Main Group compounds

Bonding polarity (ionic, polar covalent, covalent)
The chemical bonds formed by the elements of the main group cover a very broad range of
polarities. Depending on the difference in electronegativity between bonded atoms, the main
group elements can form ionic bonding (when the difference in χ is over 2), polar covalent
bonding (the difference in χ is more than 0.5) and covalent bonding (the difference in χ is
between 0.5 and 0).
Table: Chemical bond polarity: (rule of thumb): bonds between S-Blocks elements,
Metaloids, Non-metals)
s-Block metals Metalloids (and H) Non-Metals
Non-Metals Ionic Polar Covalent Covalent
Metalloids (and H) Polar covalent Covalent/Metallic Polar Covalent
S-block metals Metallic bond Polar covalent Ionic
The ionic bond is considered achieved when the difference of electronegativity of the atoms
is greater than 2.

89
The s-block elements have low electronegativity values (χ is less than 1.5) and form polar
bonding with the metalloids (of which χ is close to 2.0) and form ionic bonding with the non-
metals (χ = 2.0 to 4.0).
Example. Caesium fluoride, CsF (∆χ = 4.0 – 0.7 = 3.3); sodium chloride, NaCl (∆χ = 3.0 –
0.9 = 2.1) are regarded as having typical ionic bonding.
The s-block elements form ionic hydrides with hydrogen. Formally ionic hydrides contain a
metal cation and hydride ion H-, (the s-block element give its electron to a hydrogen which
get reduced into H- a hydride of oxidation number -1). Ionic hydrides are extremely reactive
towards water, and are moisture sensitive (they can be used as drying agents).
Example: NaH (∆χ = 2.1- 0.9 = 1.2)
NaH + H2O H2 + NaOH ∆H = -83.6 kJ/mol
Acid/base properties (Brønsted-Lowry and Lewis acidity)
Brønsted-Lowry definition of acids/bases is based on proton exchange (acids are proton

donors, base are proton acceptors). The strength of an acid or a base depends on its
dissociation in water.
Strong acids dissociate totally in water giving H 3 O+.
Example: Sulfuric acid (H 2 SO 4 ).
H2SO4 + H2O HSO4- + H3O+
Strong bases dissociate totally in water giving OH-.
Example: Sodium hydroxide (NaOH) dissociates totally in water giving OH- and Na+
NaOH Na+ + OH-

Weak acids dissociate only partially in water, and are in equilibrium with H 3 O+.
Example: Hydrofluoric acid, HF, is the only hydrohalic acid that is not considered a strong
acid. HF is a highly corrosive acid, capable of dissolving many materials including oxides
and glass but it is a weak acid because of its lower dissociation constant in water:
HF + H2O F- + H3O+ pKa = 3.17
Weak bases dissociate only partially in water, and are in equilibrium with OH-
Example: Ammonia NH 3
NH4+ + OH
-
NH3 + H2O
Lewis acid/base concept is based on electron pair (ep) donor/acceptor properties: acids are
ep acceptors, bases are ep donors:

90
Acids: electron deficient species are acceptors of electron pairs: BF 3 , H+ .

Bases: electron rich species – with at least one lone pair available – are donors of
electrons pairs: NH 3 , H 2 O.
Redox properties
Oxidising agent (reduced during the redox process: they gain electrons). A strong oxidant
increases its stability by gaining extra electron(s).
E.g. Permanganate ion MnO 4 -:
MnO4- + 8H + 5 e
+ - 2+
Mn + 4 H2O
VII II
Bromate ion: BrO 3 -
BrO3- + 6H+ + 6e- Br- + 3 H2O

V -I
Fluorine: F 2
- -
F2 + 2e 2F
0 -I
Reducing agents (oxidised during the redox process: they lose electrons). A strong reducer
increases its stability by losing electron(s).
Sodium metal: Na.

+ -
Na Na + e
0 I
Hydride H-.
H- 1
/2 H2 + e-
-I 0
4.3 Chemistry of Hydrogen H
4.3.1. Properties
Hydrogen is the most abundant element in the universe. Most of the hydrogen on earth
occurs bonded to oxygen (H 2 O) or to carbon (hydrocarbons and other organic molecules).
Electronic configuration: 1s1
Bond energy. The bond energy is the amount of energy required to break one mole of
molecules into their individual atoms. The H-H bond is one of the strongest single bonds:
only H-F (567kJ/mol) and O-H (463 kJ/mol) are stronger than H-H. The molecule of H 2 is
thus a relatively stable molecule.

91
Bond energy
H2 2H E ∆H = 436 kJ/mol
Ionisation energy. The amount of energy required to remove an electron from the atom in
its gaseous state. H ionisation energy is very high; in fact similar to O and Cl IE :1313
and1251 kJ/mol respectively. Therefore, H+ is difficult to form and has in fact no separate
chemical existence: it is always in a combined form and will migrate from one atom to
another. For example it forms H 3 O+ with water.
Ionisation energy
H H+ + e- IE ∆H = 1309 kJ/mol
Electron affinity. The amount of energy released when an electron is added to a neutral
atom to form a negative ion.
Electron affinity
H+e
- -
H EA ∆H = -71 kJ/mol
Hydrogen forms ionic hydrides with the reactive s-block metals (groups 1 and 2) and forms
covalent hydrides with the p-group metals, e.g. Al and Sn (group 13 and 14).
Electronegativity χ = 2.1. The value is intermediate in the electronegativity scale that spans
from 0.7 to 4.0.
H can form hydrides (negatively charged H) with a whole range of polarity, from ionic
hydrides Cs-H (∆χ = 1.4) to non-polar covalent hydrides B-H (∆χ = 0.1).
H can form hydrogen compounds (H is positively charged) with a whole range of polarity,
from ionic hydrogen halides HF (∆χ = 1.9) to non-polar covalent C-H (∆χ = 0.4).
4.3.2. Compounds of Hydrogen

4.3.2.1. Ionic hydrides (compounds of H-) form with very reactive s-block metals (NaH,
CaH 2 from Na and Ca), the metal atoms increase their stability by giving all their valence
electrons to the hydrogen forming a negatively charged hydride ion H-. Hydrides ions are
strong reducing agent (they readily give away their electron).
4.3.2.2. Covalent hydrides (compounds of Hδ-)
The covalent hydrides form infinite lattice solids with p-group metals
Example: with aluminum, AlH 3 (∆χ = 0.59)
They form discrete molecular species (which could be solids, liquids or gases) with the non-
metals.

92
Example: Phosphine is a odourless, colourless, flammable and toxic gas.
PH3 (∆χ = 0.01)

P
H
H
H
phosphine
4.3.2.3. The stability of hydrides decreases down any group of the periodic table.
PH 3 and AsH 3 are stable but decompose on warming: SbH 3 and BiH 3 are unstable at room
temperature. As the differences in electronegativity increase, the strength of the M-H bond
decreases due to poorer orbital overlap.
Phosphine, PH 3 (∆χ = 0.01) is a flammable but stable gas at room temperature, it

decomposes into P 4 gas at 650oC.
Arsine, AsH 3 (∆χ = 0.02) is stable kinetically but not thermodynamically. It decomposes to
produce arsenic at 230oC but is stable at room temperature.
Stibine, SbH 3 (∆χ = 0.15) decomposes slowly at room temperature to form antimony metal.
Bismuthine, BiH 3 (∆χ= 0.18) is unstable and decomposes to produce bismuth metal well
below 0oC.
Stoichiometry of hydrogen compounds of periods 2 and 3.
G1 G2 G13 G14 G15 G16 G17

Period 2 LiH BeH 2 BH 3 CH 4 NH 3 H2O HF
B2H6
Period 3 NaH MgH 2 AlH 3 SiH 4 PH 3 H2S HCl
Ionic Polymeric Discrete Covalent
hydrides Molecules
Covalent
Solid
Hydrogen compounds (except with group 13) follow the stoichiometry expected from the
octet rule.
• With group 1 and 2: both the metal and hydrogen achieve noble gas structures by
forming ionic hydrides.
• With group 14 to 17: both atoms achieve noble gas structures by forming covalent
molecules.
• With group 13: there is an anomaly due to the lack of valence electrons to satisfy the
octet rule and the valence of hydrogen.

93
With boron, the stoichiometry is 3 but borane (BH 3 ) forms gaseous dimmers: diborane
(B 2 H 6 ) with bridging H atoms (3 centre 2-electron bonds).
empty orbital bridging H
H H H
H H H 131 pm
H H o
97 H
B o
+ B B B B 120
B
H H H H H H
o
H H 83
119 pm H
dimer B2H6
With aluminium, the stoichiometry is 3, aluminium hydride (or alane) is a polymeric covalent
solid of stoichiometry: AlH 3 . In alane, each aluminium atom is surrounded by six hydrogen
atoms that bridge to six other aluminium atoms
4.3.2.4. Interstitial hydrides
Interstitial hydrides exist within metals or alloys, they are usually non-stoichiometric, with
variable amounts of hydrogen atoms in the lattice.
Example: Palladium absorbs up to 900 times its own volume of hydrogen at room
temperature, forming palladium hydride PdHx (potential application in H 2 storage).
4.3.3. Hydrogenation Reactions

Hydrogenation is a chemical reaction between molecular hydrogen and other compounds.
Hydrogen is used as a reducing agent: hydrogenation generally occurs in the presence of a

catalyst. The process is employed to reduce or saturate organic compounds (ketone,
alkynes) into alcohols and alkanes respectively.
Hydrogen is an oxidizing agent when reacting with metals to form hydrides.

94
HX
hydrogen halides
H H
X2
C C
H H
alkane
N2 cat ∆, cat
NH3
high P
H2
ammonia
O
∆, cat
M
∆ MxOy H
∆ C
MHx OH
hydrides alcohol
M + H2O
4.3.4. Production of Hydrogen

About 50 million tons of hydrogen is produced every year, more than 90% of which is made
from fossil fuels (by steam reforming, partial oxidation of oil, coal gasification) and about 4%
is by electrolysis of water.
• Steam reforming of hydrocarbons is a common method of producing bulk

hydrogen. It is performed at high temperature (600 to 1000oC) in the presence of a
metal based catalyst: steam reacts with methane to give carbon monoxide and
hydrogen.
600 - 1000oC
CH4 + H2O CO + 3 H2
Cat (Ni/Al2O3)
Additional hydrogen can be recovered by a lower temperature gas-shift reaction with

the carbon monoxide produced.
o
1) 350 C
2) 190-210oC
CO + H2O CO2 + H2
• Partial oxidation of heavy oil occurs when a sub-stoichiometric fuel-air mixture is

partially combusted in a reformer, creating a hydrogen-rich syngas (mixture of
hydrogen and carbon monoxide). Syngas can be used as fuel for internal combustion
engines. Alternatively, more hydrogen can be recovered by the lower temperature
gas-shift reaction.
2 CnH2n+2 (l) + n O2 (g) 2(n+1) H2 (g) + 2n CO(g)
CO (g) + H2O (g) H2 (g) + CO2 (g)
• Coal gasification is the process of producing syngas from coal and water with air
and oxygen.

95
3 C(s) + O2 (g) + H2O (l) H2 (g) + 3 CO (g)
• Electrolysis of water is the decomposition of water into oxygen and hydrogen gas
resulting from an electric current.
H2O H2 (g) + 1/2 O2 (g)
This is an expensive process but the majority of the hydrogen produced through
electrolysis is in fact a side product in the production of chlorine.
2 NaCl + 2 H2O Cl2 + H2 + 2 NaOH
• Biological production, using bioreactors with green algae in water, bacteria and
archaea growing on biomass. These processes are still being developed.
Green algae, such as C. reinhardtii can switch from oxygen production (as part of the
photosynthetic metabolism) to hydrogen production when growing in absence of sulfur.
Some bacteria and archaea produce hydrogen gas as part of their normal metabolism;
they can produce hydrogen from biomass.
4.3.5. Industrial uses of Hydrogen

Ammonia synthesis. The largest application of H 2 is in the production of ammonia; the
hydrogen reacts with nitrogen in presence of a catalyst to form anhydrous liquid ammonia.
3 H2 + N2 2 NH3
catalyst
Oil refineries. Large quantities of H 2 are needed in the petroleum industry, for the
upgrading of fossil fuels.
Hydrodealkylation (example: hydrodealkylation of toluene into benzene)
CH3
40-60 atm
+ H2 + CH4
o
500-600 C
toluene benzene
Hydrodesulfurisation (example: hydrodesulfurisation of ethanethiol into ethane and

hydrogen sulfide)
catalyst
C2H5SH + H2 C2H6 + H2S
Hydrocracking is a catalytic cracking process obtained at high partial pressures of

hydrogen. Hydrocraking is used for the removal of sulfur and nitrogen hetero-atoms from
hydrocarbon streams.
MeOH synthesis. Hydrogen is used as a hydrogenating agent to produce methanol from

carbon monoxide. The process takes place at high pressure (50-100 atm) and at 250oC.

96
50-100 atm
CO + 2 H2 CH3OH
o
250 C
Hydrogenation of vegetable oil into saturated fats. Hydrogen is used in the food
processing industry, as a hydrogenating agent, to increase the level of saturation of
unsaturated vegetable fats and oils.
4.3.6. Reactions of Main Group Hydrides

The chemistry of hydrogen compounds changes with periodic trends (electronegativity and
size) across the periodic table.
Hydrides of group 1 and 2 are strong reducing agents and can react violently with water.
NaH(s) + H2O(l) Na+(aq) + OH-(aq) + H2(g)
Hydrides of group 13 are mild reducing agents, Diborane reacts with water to form
hydrogen and boric acid (antiseptic and insecticidal).
B2H6(g) + 6 H2O(l) 2 H3BO3(aq) + 6 H2(g)
Hydrogen compounds of group 14 are covalent and their polarity increases down the
group. As the electronegativity decreases down the group (χ C = 2.5; χ Si =1.8, χ Ge =1.8) the
partial charge on the hydrogen goes from positive (with C) to negative (with Si, Ge, Sn) as
the polarity increases.
Example: comparing methane and silane.

Methane (CH 4 ) is a very stable molecule, the C-H bond is covalent with very little polarity
(hydrogen has a small partial (+) charge) and methane reacts with oxygen (combustion of
methane) but does not react with water.
Silane (SiH 4 ) ignites spontaneously in air and reacts instantly with water. The Si-H bond is
more polar than C-H and hydrogen has a partial (-) charge. As the central atom gets larger,
water molecules can access it easily.
SiH4(g) + 2 H2O(l) SiO2(s) + 4 H2(g)
Hydrogen compounds of group 15. Hydrogen forms covalent bonds with nitrogen (in
which the small polarity gives a slight positive charge to the hydrogen), and forms hydrides
of increasing polarities down the group (from P, to As, and Sb) as the electronegativity
decreases.
Ammonia (NH 3 ) dissolves in water to give weakly basic solutions.

97
+ -
NH3(g) + H2O(l) NH4 (aq) + OH (aq)
Phosphine (PH 3 ) is a very weak base with a low solubility in water. It spontaneously ignites
in air.
Hydrogen compounds of group 16. Hydrogen forms polar covalents bonds with the
elements of group 16, the polarity of which decreases down the group (from O, S, Se, to Te).
They do not react with water. For example, hydrogen telluride (H 2 S) is only weakly acidic
and is a gas above -1oC.
Hydrogen compounds of group 17. Hydrogen forms polar bonds with the elements of
group 17: all are acids in water (HF is a weak acid due to its poor dissociation in water, but
all the others are strong acids.
4.3.7 . Hydrogen Bonding

Covalent bonds between hydrogen and N, O, F or Cl are highly polarised resulting in the
hydrogen holding a large (+) partial charge.
Hydrogen bonding is a strong electrostatic interaction that occurs between the positively
charged hydrogens and negatively charged atoms (N, O, F, Cl) within the same molecule
(intramolecular bonding) or between two molecules (intermolecular bonding).
Intramolecular hydrogen bonding is responsible for the shapes and functions of many
macromolecules such as proteins and DNA.
Intermolecular hydrogen bonding is the strongest intermolecular force (20 to 100 kJ.mol-1).
Intermolecular hydrogen bonds are responsible for the 3D structure of ice water and for the
high boiling point of water.
When comparing boiling points down the elements of the group 16:
(H 2 O (100oC); H 2 S (-60oC); H 2 Se (-41.25oC), H 2 Te (-1oC)), H 2 O seems abnormally high.
This is because the hydrogen bonds create a cohesion amongst the water molecules in the
liquid form which prevents them from escaping into a gaseous form. This must be overcome
to generate gaseous H 2 O, hence the higher temperature required.
Boiling point (oC)
H2O
100
0 mass
H2Te
H2Se
H2S
-100

98
4.4. Chemistry of the Halogens (group 17)

4.4.1. Properties
Halogens have seven valence electrons and a valency of one: they form diatomic halogen
molecules such as F 2 , Cl 2 , Br 2 , etc .
Example: Fluorine (F 2 ) has a very weak F-F bond (BDE is only 159 kJ.mol-1). The small bond
length results in inter-electronic repulsions between lone pairs, weakening the F-F bond.
Halogens have the highest electronegativity values in their respective period going from At
(χ = 2.2) to F (χ = 4.0).
They are strong oxidants. Halogens have a high affinity for electrons (EA) and form stable
halide ions (X-) with hydrogen and metals.
4.4.2. Production of Halogens

Fluorite (CaF 2 ) is the main mineral source of commercial fluorine.
Cryolite (Na 3 AlF 6 ) is the least abundant but the most concentrated mineral source of
fluorine.
Fluorine (F 2 ) is produced by electrolysis of a KF/HF mixture. HF alone cannot be

electrolysed, the presence of some KF is critical even though it is not consumed in the cell
and remains in solution. When combined, potassium fluoride (KF) and hydrogen fluoride
(HF) produce potassium bifluoride (KHF 2 ), which increases the conductivity of the solution.
2 HF(l) H2(g) + F2(g)
Chlorine (Cl 2 ) is produced by electrolysis of NaCl aqueous solution.
reaction at anode 2Cl-(aq) Cl2(g) + 2e-
reaction at cathode 2 H2O + 2e- 2 OH-(aq) + H2(g)
2 Cl-(aq) + 2 H2O Cl2(g) + 2 OH-(aq) + H2(g)
Note. During the process H 2 and NaOH are also produced.
+ -
2 Na (aq) + 2 Cl (aq) + 2 H2O Cl2(g) + 2 NaOH(aq) + H2(g)
Bromine (Br 2 ) and Iodine (I 2 ) are produced by chlorine oxidation of halide compounds
containing (Br- or I-).
- 100-120oC -
2 Br (aq) + Cl2(g) Br2(g) + 2 Cl (aq)
Note. It is necessary to heat the system to prevent the bromine from remaining in solution.

99
4.4.3. Industrial use of Halogens

Fluorine (F 2 )
Over half of the production of fluorine is used in uranium separation. Uranium is turned into
gaseous uranium hexafluoride to separate uranium-235 (required for nuclear fission) from
the heavier isotope uranium 238.
Polytetrafluoroethylene (PTFE) production. PTFE (DuPont’s Teflon) is an important

substance with applications in electrical insulation, as a dielectric. It is also used in the
chemical process industry in coating pipes, tubing, jointing materials, etc - where corrosion
resistance in needed.
Chlorofluorocarbons (CFCs) used as refrigerant gases, were the major class of fluorinated
organic chemical in the 1980’s. Hydrochlorofluorocarbons and hydrofluorocarbons (HFCs)
have now replaced CFC as refrigerants, following concerns about their environmental impact
(see chapter 4.6).
Several million tons per years of sodium fluoride (NaF) is produced globally. NaF has many
applications: it is used in dentistry, in water treatment and as a cleaning agent.
Chlorine Cl 2
The production of industrial and consumer products, such as plastics, solvents, textiles,
insecticides, are the principal applications of chlorine (70% of production).
Organochlorine intermediates are used in the production of many important industrial

materials such as polycarbonates and polyurethanes.
Sanitation and water treatment uses about 20%, in bleaches and disinfection products
preparation.
The production of inorganic material (such as hydrogen chloride (HCl), dichlorine monoxide
(Cl 2 O), hypochlorous acid (HOCl), etc) uses about 10%.
Bromine Br 2
Brominated flame retardants (BFRs) represent the largest commercial use of bromine (27%).
BFRs are organobromide compounds that have inhibitory effects on the ignition of
combustible organic materials. They are effective in plastics and textile applications.
Ethylene di-bromide (BrCH 2 -CH 2 Br) was historically used as an anti-knock fuel additive. It
reacts with lead residues to generate volatile lead bromides, preventing fouling of engines.
About 15% of bromine is used for the preparation of agricultural chemicals. For example,
methyl bromide or ethylene bromide, both poisonous, have been used as pesticide to treat
soils and houses.
Iodine I 2
The largest part of iodine production is consumed by the production of ethylenediammonium
diiodide (EDDI) a nutritional supplement for livestock.
Iodine is also consumed in the synthesis of acetic acid in which iodine is a co-catalyst.
About half of the iodine produced is used in the production of a range of organic chemicals.

100
Potassium iodide (KI) is produced for medical application and consumes about 15% of the
iodine production. KI has been used as an expectorant and is currently used to treat acute
thyrotoxicosis.
15% used directly as I 2 ; 15% other Iodide salts.
4.4.4. Common stoichiometries of the Halides of period 2 and 3

Stoichiometries of the fluorides
G1 G2 G13 G14 G15 G16 G17 G18
LiF BeF 2 BF 3 CF 4 NF 3 OF 2 F2
NaF MgF 2 AlF 3 SiF 4 PF 3 SF 2 ClF

PF 5 SF 4 ClF 3
SF 6 ClF 5
Stoichiometries of the chlorides

G1 G2 G13 G14 G15 G16 G17 G18
LiCl BeCl 2 BCl 3 CCl 4 NCl 3 OCl 2 ClF
NaCl MgCl 2 AlCl 3 SiCl 4 PCl 3 S 2 Cl 2 Cl 2

PCl 5 SCl 2
• The stoichiometries of halides are mostly similar to that of the hydrides.

• The chemical reactivity of halides varies dramatically along the periodic table (NaF
and OF 2 ). (Do not mistake OF 2 for NaF! NaF is used in toothpaste and OF 2 is a
powerful fluorinating agent).
• The halides of group 1 and 2 are ionic halides, when the halides of other groups are
polar covalents.
• The elements of the second period strictly obey the octet rule but the elements from
the third period (and higher) have access to extra orbitals to expand their electronic
configuration, resulting in possible hypervalency.

101
Example: PF 3 (obeys the octet rule) and PF 5 (hypervalent).

upe
F [He] 2s2 2p5
s p d
2 3 0
Ground state P [Ne] 3s 3p 3d
sp3
Hybridisation sp3
P
F F
F
Phosphorus in PF 3 obeys the octet rule: P sp3 hybridisation provides four valence orbitals
(three bonding to F and a lone pair). The total number of electron around the P is 8.
Because an empty 3 d-orbital is available, the phosphorus can also undergo excitation to
promote one electron from the 3s-orbital to one empty 3d-orbital, providing five unpaired
electrons and allowing the formation of a PF 5 molecule (here the P is hypervalent: it is
surrounded by 10 valence electrons.
s p d
Excited state P 1 3 1
[Ne] 3s 3p 3d
sp3d
3
Hybridisation sp d of P 10 ve arround P
F P F
F F
PF 5 does not obey the octet rule: phosphorus sp3d hybridisation provides five valence
orbitals for bonding with five F. As a result 10 valence electrons surround the central
phosphorus.
Hypervalency is possibe for the elements of period 3 and over and is common for the
elements of group 15, 16 and 17 (and also 18: for example the fluorides of noble gases such
as XeF 4 )
More on hypervalency (see previous topic: Chapter 3.2.2)

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4.4.5. Hydrogen halides

Hydrogen halides are strong acids (except H-F which is a weak acid as it does not dissociate
well in water).
H-F and H-Cl are major industrial chemicals.
Hydrofluoric acid (H-F) is produced by the treatment of the mineral fluorite (CaF 2 ) with
concentrated sulfuric acid:
CaF2(s) + H2SO4(l) CaSO4(s) + 2HF(g)
H-F solution reacts with SiO 2 , (H-F attacks glass, used in etching):
6 H-F (aq) + SiO2 (s) 2 H+ (aq) + SiF62- (aq) + 2 H2O (l)
H-F is used as a catalyst in oil refining and is an intermediate in the synthesis of many
organofluorine compounds.
Hydrogen chloride H-Cl is prepared by direct reaction of H 2 and Cl 2 gases.
UV light
Cl2(g) + H2(g) 2 HCl(g)
H-Cl can also be prepared in the laboratory (in small amounts) from the reaction of NaCl with
H 2 SO 4 .
NaCl + H2SO4 NaHSO4 + HCl
4.4.6. Halogen oxyacids

Halogen oxyacids are polyatomic acids that contain oxygen, halogen and at least one
hydrogen atom.
Acid Name of Acid Anion Name of Anion Cl ox. no.
-
H-O-Cl hypochlorous ClO hypochlorite 1+
H-O-ClO chlorous ClO2- chlorite 3+
H-O-ClO2 chloric ClO3- chlorate 5+
H-O-ClO3 perchloric ClO4- perchlorate 7+

103
Applications: Halogen oxyacids are strong oxidizing agents.

• Calcium hypochlorite [Ca(ClO) 2 ] is used in swimming pools for water treatment.
• Sodium chlorite (NaClO 2 ) is a major component of liquid bleach.
• Sodium chlorate (NaClO 3 ) is used in the paper making industry as a bleaching agent
for pulp.
• Sodium perchlorate (NaClO 4 ) was used as a solid-fuel booster for the US space
shuttle: - each launch used about 700 tons.
4.4.7. Interhalogen Fluorides

Interhalogen fluorides contain fluorine and other halogen atoms (chlorine, bromine, iodine or
astatine).
They are subject to hydrolysis and ionize into polyhalogen ions.
The general formula is XY n , with the most electronegative halogen placed last.
Example: Interhalogen fluorides (XF n ).
Oxidation Fn ClF n BrF n IF n

number of X
0 F2
1 ClF BrF IF
3 ClF 3 BrF 3 IF 3
5 ClF 5 BrF 5 IF 5
7 IF 7
The geometry of interhalogen fluorides obeys the VSEPR theory.
Formula Lewis structure VSEPR geometry
XF X F AXE3, tetrahedral X
F
F
F F
XF3 X F AX3E2, trigonal bipyramidal X F
F
F
F
F F
F
XF5 F X F AX5E, octahedral X
F F
F F
F
F F F
F
XF7 X F AX7, pentagonal bipyramidal X F
F
F F
F F
F

104
Note. In the interhalogen general formula (XY n) ; X represents the less electronegative
halogen (with fluorides, X = Cl, Br, I). In the VSEPR geometry AXnEm, X represents the
number of F. Not to be confused.
4.5. Chemistry of the Chalcogens (group 16: O, S, Se)

The chalcogens are the elements of the oxygen family or group 16. All chalcogens have six
valence electrons and their most common oxidation states are -2, +2, +4 and +6.
The focus of this course is comparison between the elements O and S.
4.5.1. Production
The main method of oxygen (O 2 ) production is by fractional distillation of liquefied air. About
100 million tons of O 2 are produced annually for industrial uses.
Sulfur is either mined or recovered from oil refineries; about 68 million tons are produced
annually.
4.5.2. Stoichiometry of most common oxides of period 2 and 3

G1 G2 G13 G14 G15 G16 G17 G18
Li 2 O BeO B2O3 CO 2 N2O O2 F2O
CO NO O3 F2O2
N2O3
NO 2
N2O5
Na 2 O 2 MgO Al 2 O 3 SiO 2 P4O6 SO 2 Cl 2 O
P 4 O 10 SO 3 Cl 2 O 2
4.5.3. Reactivity of Alkali metals with O2, H2O,

Alkali metals react with O 2 to give oxide (M 2 O), peroxide (M 2 O 2 ) or superoxide (MO 2 ).
The relative stability of these species depend on the size of the metal ion (larger cations
stabilize larger anions):
• Small ions (Li) form stable oxides (Li 2 O)
• Medium size ions (Na) form peroxides (Na 2 O 2 )
• Large ions (K, Rb, Cs) form superoxides (KO 2, RbO 2, CsO 2 )
The oxides of group 1 and 2 react with water to give basic solutions.
Example with Li 2 O.
+ -
Li2O (s) + H2O (l) 2 Li (aq) + 2 OH (aq)
The oxides of non-metals (except CO) react with water to give acidic solutions.
Example with SO 3 .
SO3 (s) + H2O (l) 2 H+ (aq) + SO42- (aq)

105
The oxides of the other metals do not react with water, but react with both acids and
bases: they are amphoteric.
Example of Al 2 O 3 .
+ 3+
Al2O3 (s) + 6 H (aq) 2 Al (aq) + 3 H2O (l)
-
Al2O3 (s) + 2 OH (aq) + 3 H2O (l) 2 Al(OH)4- (aq)
4.5.4. Oxides of group 14 (C, Si)

The elements of group 14 form very strong bonds with oxygen.
The oxides of carbon (CO 2 and CO) are both discrete molecules of gases under standard
conditions of temperature and pressure, and are both thermodynamically stable.
Carbon dioxide (CO 2 ) is a byproduct of fossil fuels combustion. Carbon dioxide is also a
useful product: about 30 million ton a year is used industrially: 50% as a refrigerant (dry ice)
and 25% for the preparation of fizzy drinks.
Carbon dioxide is a potent greenhouse gas: it traps solar radiation in the atmosphere. (ref:
see later discussion in chapter 4.6.3).
O C O
carbon dioxide
Carbon monoxide (CO) is a highly toxic gas. CO forms when carbon compounds burn in
deficiency of O 2 . The toxicity is due to the fact that CO molecules bind to the iron centre of
haemoglobin and prevent O 2 from binding to it: this affects oxygen transport throughout the
body.
C O C O
carbon monoxide

106
Silicon dioxide (SiO 2 ). is not a discrete molecule like CO 2 and CO, but makes extended
lattice solids. SiO 2 can be amorphous or crystalline and has many different crystal
structures. SiO 2 is most commonly found in nature as sand or quartz.
Unlike carbon, silicon does not form strong π-bonds with oxygen, because the overlap
between the Si 3p and the O 2p is relatively poor. Instead, Si forms four σ-bonds with four O
atoms and each O is further linked to another Si by σ-bonds.
Si
O
O
O
Si
O Si
Si O
O O
O
O
3D structure of silicon dioxide (SiO2)
Zeolites are microporous aluminosilicate minerals, used as commercial adsorbents and

molecular sieves. They are used in water purification which is the single biggest use of
zeolites: to "soften" water (to reduce the concentration of ions in water). Zeolites are also
used in gas separation and as catalysts in nuclear reprocessing.

107
4.5.5. Oxides of group 15 (N, P, As)

The most important members of this group are nitrogen and phosphorus.
Oxides of Nitrogen.
There are five oxides of nitrogen, with N ranging in oxidation number from +1 to +5
N 2 O, NO, N 2 O 3 , NO 2 , N 2 O 5 .
Ox. Formula Note Lewis structure

No.
+1 N2O Laughing
gas N N O
+2 NO toxic
N O
+3 N2O3 Blue liquid O
N N
O O
+4 NO 2 In
equilibrium O O
with N 2 O 4 2 O N O N N
O O
+5 O O O
N2O5 O
N N N
N
O O O O O
O
In equilibrium with NO 2 + +NO 3 -

108
There are also two important oxoacids of nitrogen: nitrogen(III) acid (nitrous acid) HONO and
nitrogen(V) acid (nitric acid) HNO 3 .
Nitric acid (HNO 3 ) is produced in nature when NO 2 reacts with water. Nitric acid is highly
reactive, and behaves as an oxidising agent and a nitrating agent as well as an acid.
Industrial quantities of nitric acid are produced using the Ostwald Process.
Pt catalyst NO (g) + 3/2 H2O (g)

NH3 (g) + 5/4 O2 (g)
5 atm
850oC
NO (g) + 1/2 O2 (g) NO2 (g)
3 NO2 (g) + H2O (l) 2 HNO3 (aq) + NO (g)
Nitric acid is an intermediate in the synthesis of NH 4 NO 3 , an important fertiliser.
Oxides of Phosphorus.
The two most common oxides of phosphorus are phosphorus(III) oxide P 4 O 6 and
phosphorus(V) oxide P 4 O 10 . Both have a P with sp3 hybridisation. Phosphorus(V) oxide also
has p-d π-bonds between P and O.
Reaction with water.

O
P4O6 (s) + 6 H2O (l) 4 H3PO3 (aq)
P
HO
H
HO
phosphorous acid
O
P4O10 (s) + 6 H2O (l) 4 H3PO4 (aq)
P
HO
OH
HO
phosphoric acid

109
4.5.6. Oxides of Sulfur

Sulfur dioxide (SO 2 ) and sulfur trioxide (SO 3 ) are commercially and environmentally
important. Both have a sp2 hybridised S and both have pπ : dπ bonding between S and O. S
is hypervalent in both products.
Sulfur dioxide is a toxic gas. It is released by volcanic activities and because coal and
petroleum contain sulfur compounds; their combustion generates sulfur dioxide.
Sulfur dioxide can further oxidise into SO 3 in the presence of NO 2, and forms sulfuric acid
(H 2 SO 4 ) which is partly responsible for acid rain.
Sulfur dioxide is an intermediate in the industrial production of sulfuric acid H 2 SO 4 . The

conversion of SO 2 into H 2 SO 4 is achieved using the “Contact Process”.
S8 (s) + 8 O2 (g) 8 SO2 (g)
2 SO2 (g) + O2 (g) 2 SO3 (g)
SO3 (g) + H2O (l) H2SO4 (aq)
Application of sulfuric acid.

Annual production was 157 million tons in 2000
About 60% is used in the production of H 3 PO 4 (a fertilizer)
Other uses include oil refining, steel manufacturing.
Table. Comparison of oxygen and sulfur chemistry:
Oxygen Sulfur
Electronegativity χ = 3.44 χ = 2.58
much more electronegative
Formal oxidation number mostly −2 variable (-2 to +6)
but with exceptions, e.g.:
0 in O 2 , -1 in H 2 O 2
Hybridisation sp3 (H 2 O) sp3 (H 2 S, SF 2 )
sp2 (CO 2 ) sp3d (SF 4 )
sp3d2 (SF 6 )

110
4.6. Environmental Impact of Main Group Compounds

The three mains areas where the main group compounds have a harmful environmental
impact are: acid rain, ozone depletion and greenhouse effect.
All these effects are different and are not to be confused.
4.6.1. Acid rain

Acid rain is caused by emissions of sulfur dioxide and nitrogen oxide. When these react with
water in the atmosphere they produce sulfuric acid. The acid rain cause great damage to the
economy, e.g. steel structure (bridges) corrosion, erosion, paint peeling.
SO 2 is produced from the oxidation of sulfur compounds, and is produced during the
combustion of coal and oil when they contain sulfur (this leads to concerns over the use of
high-sulfur coal). Sulfur dioxide reacts with water to give H 2 SO 3 , a relatively weak acid.
SO2 (g) + H2O (l) H2SO3 (aq)
The problem happens when sulfur dioxide oxidizes in the atmosphere into SO 3 . Sulfur
trioxide then reacts with atmospheric water to give sulfuric acid.
2 SO2 (g) + O2 (g) 2 SO3 (g)
SO3 (g) + H2O (l) H2SO4 (aq)
Nitric acid is formed from various nitrogen oxides “NOx”, primarily NO and NO 2 .
Acidity of the rain.

• Normal rain is slightly acidic, because of solubilised CO 2 : its pH is 5.6.
• Acid rains are much more acidic (pH 4.2, in some part of the USA; pH 2.7has been
measured in Sweden).
• The world record was established in West Virginia (USA) in 1980 with pH 1.8.
Effect of the acidity

• Fish/shellfish start to die at pH 5.0 to 4.5
• Forests are harmed (nutrients are removed and toxic substances are released by
acidity).
Technical solutions
• Scrub exhaust gases to remove acidic oxides.
SO 2 can be removed with alkaline materials, such as CaO or NaOH.
NOx converted to HNO 3 .
• Chemically treat acidified lakes (using CaO)
• Catalyse noxious products into more benign species.
Catalytic converters on cars catalyse the transformation of CO into CO 2 , NOx into
N 2 , and O 2 and unburnt hydrocarbons into CO 2 .

111
4.6.2. Ozone depletion
The surface of earth is continually bombarded by solar radiation. The ozone layer absorbs
UVB ultraviolet light (280-320nm) from the sun and therefore protects us. UVB photons have
enough energy to break chemical bonds, and damage our DNA which leads to skin cancer.
It is feared that the ozone depletion will lead to an increase in skin cancer.
Ozone cycle
Three allotropes of oxygen are involved in the ozone-oxygen cycle: O (atomic oxygen), O 2
(oxygen gas) and O 3 (ozone gas).
Ozone is formed in the stratosphere when oxygen molecules photo-dissociate after

absorbing an ultraviolet radiation (λ less than 240 nm). This converts a single O 2 molecule
into two highly reactive oxygen atoms.
UV light
O2 2O
Each oxygen atom then combines with a O 2 molecule to create O 3 .
O + O2 O3 ozone formation
Ozone molecule absorbs UV light and splits into a molecule of O 2 and an oxygen atom.
UVB
O3 O + O2 ozone breakdown
This is a continuing process that terminates when an oxygen atom recombines with an
ozone molecule to make two O 2 molecules.
O + O3 2 O2 termination

112
The effects of chlorofluorocarbons on ozone.

Chlorofluorocarbons (CFCs), such as CF 2 Cl 2 , were previously used as aerosol propellants,
plastic foam blowing agents, and air-conditioning refrigerants, - had to be replaced due to
their effect on ozone.
Paradoxically, CFCs are very stable in lower atmosphere. However, when in the
stratosphere; high energy UV radiations break the C-Cl bonds and form chlorine radicals Cl.,
which are extremely reactive.
high UV
CF2Cl2 CF2Cl + Cl (Cl is extremely reactive)
A chlorine radical Cl. reacts with ozone to form a chlorine monoxide radical (.ClO) and
oxygen. The chlorine monoxide radical can go on to react with an oxygen atom to form
oxygen and generate more chlorine radicals.
O3 + Cl ClO + O2
ClO + O Cl + O2
In this way, the overall reaction for the decomposition of ozone into oxygen is a
radical chain process initiated by chlorine radicals. The radical chain process via
chlorine radical has a 2 year lifetime.
Technical solutions.
CFCs are replaced as aerosol by other gases such as butane, and as refrigerants by HFCs
(hydrofluorocarbons such as CF 3 CH 2 F) although these too can be replaced.

113
4.6.3. Greenhouse Effect.

There is a direct correlation between the global average temperature and the atmospheric
concentration of what are now called the greenhouse gases. The three major greenhouse
gases are: water vapour (accounting for 36 to 70% of the greenhouse effect), carbon dioxide
(9 to 26%), methane (4 to 9%). Other contributors include nitrous oxide, ozone and CFCs.
Carbon dioxide
Carbon dioxide is an important contributor to the greenhouse effect.
Technical solutions
• Use less fossil fuel.

It is believed that a reduction of greenhouse effects could be achieved by reducing our
carbon dioxide emission. Reducing fossil fuel consumption could be a direct way to achieve
that outcome; although this is difficult because the worldwide energy requirement is
increasing dramatically and relying even more than before on fossil fuel consumption.
• CO 2 capture AFTER combustion.

Post-combustion capture of CO 2 is achieved by using amine solvents, using CaO or
membrane separators.
• CO 2 capture BEFORE combustion.

Pre-combustion capture of CO 2 is achieved by generating H 2 from fuel, and H 2 not the fossil
fuel itself is combusted to generate power.
• Oxy-fuel combustion
Pure O 2 is used instead of air during the combustion of a fuel. Because pure oxygen is used,
higher temperatures can be achieved and consequently less fuel is necessary. Oxy-fuel
combustion produces about 75% less flue gases compared with air-fuel combustion.
Another benefit - the reduction of nitrogen oxides produced (because nitrogen from air is not
present in the combustion).
Methane
Methane is a very effective greenhouse gas; 21 times more efficient than CO 2 . and its
importance as a greenhouse gas could have been underestimated. Methane is produced
naturally by methanogenic bacteria in the gut of ruminants.
Note. CFCs are even more effective greenhouse gases, 10,000 times more effective than
CO 2 . But their small concentration in atmosphere means they are not a significant
contributor to greenhouse effect.

114

115
TOPIC 5. ORGANIC CHEMISTRY INTRODUCTION
Topic 5
Organic Chemistry Introduction
Content
5.1. INTRODUCTION ............................................................................................... 116
5.2. ALKANES ....................................................................................................... 118
5.2.1. Structure and bonding in Alkanes ......................................................... 119
5.2.2. Drawing and writing structure for alkanes ............................................. 121
5.2.3. Isomerism in Alkanes ............................................................................ 124
5.2.4. Conformations of Alkanes ..................................................................... 127
5.2.5. Reactions of Alkanes ............................................................................ 127
5.3. HALOGENOALKANES (ALKYL HALIDES) ............................................................. 133
5.3.1. Structure and Reactivity ........................................................................ 133
5.3.2. Substitution Reactions S N 2 and S N 1. .................................................... 134
5.3.3. Elimination Reactions of Alkyl Halides E2 and E1................................. 141
5.4. ALKENES ....................................................................................................... 145
5.4.1. Structures and Reactivity ...................................................................... 145
5.4.2. Synthesis of Alkenes ............................................................................. 147
5.4.3. Reactions of Alkenes ............................................................................ 149
5.5. ALCOHOLS ..................................................................................................... 152
5.5.1. Structure, Properties, and Acid-Base Reactions ................................... 152
5.5.2. Synthesis of Alcohols ............................................................................ 159
5.5.3. Oxidation of Alcohols ............................................................................ 162
5.5.4 Grignard Reagents ................................................................................. 165
Learning objectives
Structure and bonding of simple organic compounds and an introduction to the common
functional groups found in organic chemistry including alkyl halides, alkenes and alcohols.

116
5.1. Introduction
Organic chemistry is the scientific study of carbon-based compounds and materials. As
organic compounds form the basis of life on earth, organic chemistry is the chemistry of life.
Example of organic molecules, made by living organisms: methane (bacteria), testosterone

(animal), glucose (plants).
OH OH
H
H O
C H HOHO
H H H H
OH
O OH
methane, CH4 testosterone, C19H28O2 Glucose, C6H12O6
Organic compounds are structurally diverse and are important constituents of many
consumers’ products including: plastics, pharmaceuticals, petrochemicals, food, explosives,
and paints.
Few pharmaceuticals:
NH2 O
H H
N S O
O
O N
HO OH HN
O
O NH2
O
amoxicillin, C16H19N3O5S Osteltamivir (Roche's Tamiflu), C16H28N2O4
O
H
N N
N N
H
HO O S
O
S
N O
H
N
ritonavir (Abbott Laboratories' Norvir), C37H48N6O5S2
Amoxicillin developed by SmithKline Beecham, is a β-lactam antibiotic used to treat

bacterial infections.
Osteltamivir is manufactured by Roche under the trade name Tamiflu. It is an antiviral
drug, used against influenza (flu) virus.

117
Ritonavir, commercialised by Abbott Laboratories as Norvir, is an antiretroviral drug from

the protease inhibitor class. It is used to treat HIV infection and AIDS.
Food ingredients:
HO
O N
O OCH3 N
N
H NaSO3 SO3Na
OH NH2 O
aspartame; C14H18N2O5 sunset Yellow FCF (E 110); C16H10N2Na2O7S2
Aspartame is a synthetic sweetener, used as sugar substitute in food and drinks.
Sunset Yellow is a synthetic yellow azo dye. It is a food colouring agent used in soft drinks
under the code name E110.
Explosives materials:
O
O N O
O N O O
O O N
O OO
N N O
O N N O OO
O
O N O OO O
N O O N N
O
N O n
O O
DRX, C3H6N6O6 nitrocellulose, (C6H8(NO2)2O5)n
RDX (Research Department Explosive) is an explosive nitro-amine, widely used in military

and industrial application.
Nitrocellulose was originally used as a lightweight combustible explosive material

(guncotton). Today nitrocellulose slides are commonly used for immobilizing nucleic acids in
Southern blots and northern blots.
Organic chemistry includes the study of the structure, properties and reactions of organic
compounds. A professional chemist, whether working in synthesis, in drug discovery or in
process have learnt how to analyse the structure of molecules using spectroscopic
techniques, can predict some of their properties and can understand the mechanism of how
most organic reactions work.
As part of studying the properties and reactivities of organic compounds, an organic chemist
learns to synthesise molecular structures. Very simple molecules involving few steps of
synthetic reaction to start with, and finishing with very complex molecules, such as natural
products Palytoxin, involving multistep synthesis.
Virtually any organic molecule can be synthesised, no matter how complex.

118
Palytoxin is a huge natural molecule. To achieve its total synthesis, eight separate parts
were synthesized and joined together to form the entire molecule. The synthesis of palytoxin
was called “the Mount Everest of organic synthesis” by Crawford in 1989.
Note. The introduction is for interest only and students are not expected to memorise
examples.
5.2. Alkanes
Alkanes are a subclass of hydrocarbons (compounds containing only H and C; fossil fuel).
The two main subclasses of hydrocarbons are the saturated hydrocarbons (hydrocarbons
with single bonds only) and the unsaturated hydrocarbons (all the hydrocarbons with double
or triple bonds: alkenes, alkynes and arenes).
alkanes alkenes alkynes arenes
H
H H
H H H C H
H C C H C C
C C H C C H
H H H H C C
H C H
saturated Unsaturated
aliphatic (non cyclic, non-aromatic) aromatic

119
Note. Cyclic hydrocarbons (cyclic alkanes and cyclic alkenes) are alicyclics.
5.2.1. Structure and bonding in Alkanes
Methane (CH 4 ) is the first member of the alkane family with one carbon centre. Carbon has
four valence electrons and forms a total of four single bonds with hydrogen atoms. The
geometry of methane is tetrahedral: all four bonds are equivalents in energy and their angles
are 109.5o. This geometry is due to the sp3 hybridisation of carbon. (see Topic 3).
four σ-bonds
four sp3 hybrid orbitals
Energy
2p2
3
sp
2s2
2
1s 1s2
Ground state C C hybridised CH4
Ethane (C 2 H 6 ) is the second member of the alkane family with two carbons. Each carbon
makes three sigma bonds with three hydrogen atoms and one sigma bond with another
carbon.
C-C σ bond
H H
H
C C
H
H H
ethane

120
Alkenes contain carbon-carbon double bonds. The double bond is achieved by sp2
hybridisation of the carbon. Each carbon forms three sigma bonds (two C-H and one C-C)
with three sp2 orbitals and forms one C-C pi bond from the overlap of the p-orbitals. Sp2
carbons have a trigonal planar geometry.
C-C π bond
one p orbital
2
three sp hybrid
Energy two C-H σ bonds one C-C σ bond
2
2p p
2
sp
2s
2 π bond
σ bonds
2 2
1s 1s
Ground state C C hybridised C2H6
Alkenes are rigid because the C=C double bond allows no rotation.
The p-orbitals need to be aligned to form a π-bond. Rotation would break this alignment and
therefore is highly unfavorable.
rotate
try to rotate one end of π-bond
CH3
H CH3 H H H
H3C H X H3C
H
H3C CH3
very unfavourable process
overlap between p-orbitals is lost,
π-bond is broken Cis alkene
Trans alkene
(p-orbitalsnow are 90o to each other)
Alkanes freely rotate around the C-C single bond.
rotate one end of s-bond rotate

H3C H H H3C H CH3 H3C H3C H
H easy process H easy process H

H CH3 H H H H
σ-bond is cylindricallyl symmetric overlap between sp3-orbitals is not affected by rotation

121
Example:
H H H H H
H
H H H
H
ethane spins freely ethylene is flat and rigid
can rotate around C-C bond no rotation around C=C bond
Names and molecular formulae of linear (straight-chain) n-alkanes
No. of C formula name mp bp Physical

state at RT
1 CH 4 methane -182 oC -164 oC gases at RT
2 C2H6 ethane -183 oC -89 oC
3 C3H8 propane -188 oC -42 oC
4 C 4 H 10 butane -140 oC -1.1 oC
5 C 5 H 12 pentane -130 oC 36.1 oC liquid at RT
6 C 6 H 14 hexane -96 oC 68 oC
7 C 7 H 16 heptane -90 oC 98.42 oC
8 C 8 H 18 octane -57 oC 125-126 oC
9 C 9 H 20 nonane -51 oC 151 oC
10 C 10 H 22 decane -30 oC 174.1 oC
20 C 20 H 42 icosane 36-38 oC 342.7 oC In paraffin

wax
Note. Values of mp and bp are for information only.
5.2.2. Drawing and writing structure for alkanes
E.g. Pentane, C 5 H 12 .
H H H H H
H C C C C C H CH3CH2CH2CH2CH3 CH3(CH2)3CH3
H H H H H
Lewis structure condensed structures
skeletal (line) structure of pentane

122
The line structure is used in professional publications. Lines represent the carbon
framework. In line structures, each line segment is understood to have a carbon atom at
each end, unless another atom (hetero-atom) such as oxygen or nitrogen is shown.
Hydrogen atoms attached to oxygen or nitrogen atoms are shown but not those attached to
carbon.
Multiple bonds are represented by multiple lines - just like in Lewis structure.
Chains of carbon atoms containing C-C bonds are represented in zigzag manner to indicate
the approximate shape of the molecule. Double bonds are incorporated into the zigzag
carbon chain.
How to draw molecules in “line structure”:

• Draw the chains of atoms as zig-zags.
• Miss out the Hs attached to the carbon atoms (unless there is a reason not to).
• Miss out the capital Cs representing carbon atoms (unless there is a reason not to).
• Keep the hetero-atoms (O, N, etc…) that are part of the structure and the hydrogen
atoms attached to hetero-atoms too.
For example:
Lewis structure line structure
H H H H H OH
OH
H C C C C H
H C C H
H H
O O
H C C C
OH OH
H
H C H
C C
C C
H C H
H

123
Branched alkyl groups can be abbreviated
alkyl branch branch
Me- CH3 (methyl) Ar- (aromatic)
Et- CH2CH3 (ethyl) Ph- (phenyl)
n-Pr- CH2CH2CH3 (propyl) Bn- (benzyl)
i-Pr- CH(CH3)2 (isopropyl)
n-Bu- CH2CH2CH2CH3 (butyl)
i-Bu- CH(CH3)CH2CH3 (iso-butyl)
t-Bu- C(CH3)3 (tertio-butyl)
Example:
OH OH
abbreviate Et
OH OH
abbreviate Ph t-Bu
Et
More practice: Draw the following molecules in line structure; and in line structure using
abbreviation for branched alkyl groups.
H
H C H H NH2 OH NH2 NH2
H C C C C OH or i-Pr OH
H H O O O
H C H
H
H Me
H H
H C H C
H H H O or Et OEt
C
H H C C
O C C H O O
H C H H
O

124
Remember that triple bonds between carbons atoms (which are sp hybridised) have an
angle of 180o so a linear structure.
H
H H
H C
C C C C C H
H H
H C H
H
Recommended reading about structure drawing: “Organic Chemistry” Clayden, Greeves,

Warren, OUP, 2nd Edition, Chapter 2.
5.2.3. Isomerism in Alkanes
Structural isomers are compounds which have the same molecular formula, but a different
order of attachment of the constituent atoms
CH 4 ; C 2 H 6 ; C 3 H 8 have one structural isomer only.
How many structural isomers does C 4 H 10 have?

Two structural isomers: one straight chain (n-butane) – “n” for normal-, and a branched
isomer i-butane – “I” for iso.
H H H H
H C C C C H CH3(CH2)2CH3
H H H H
C4H10, n-Butane
H
H C H
H
H C C H HC(CH3)3
H
H C H
H
C4H10, i-Butane

125
How many structural isomers does C 5 H 12 have?

Three structural isomers: one straight chain (n-pentane) ; two branched isomers.
H H H H H
H C C C C C H CH3(CH2)3CH3
H H H H H
C5H12, n-pentane
H
H C H
H H H
H C C C C H CH3CH3CH(CH3)2
H H H H
C5H12, 2-methyl butane
H
H C H
H H
H C C C H C(CH3)3
H H
H C H
H
C5H12, 2,2-dimethyl propane
How many structural isomers can C 6 H 12 have? 5!
How many structural isomers can C 25 H 52 have? 36 797 588 !
Carbons in a saturated hydrocarbon can be primary, secondary, tertiary or quaternary:
CH2 secondary carbon, CH3 primary carbon,

bonded to two other carbon bonded to one other carbon
H H
H C HH C H
H H H
H C C C C CH
H H H H
H C H
CH tertiary carbon, H C quaternary carbon,
bonded to three other carbons bonded to four other carbons

126
The terms primary, secondary, tertiary also apply to functional groups (such as alcohol) to
which a given carbon is bonded: primary alcohol (OH is bonded to a primary carbon);
secondary alcohol (OH is bonded to a secondary carbon) and tertiary alcohol (OH is bonded
to a tertiary carbon).
OH OH OH
primary alcohol secondary alcohol tertiary alcohol
Alkyl halides are also classified as primary, secondary or tertiary halides depending on
whether the halogen is bonded to a primary, secondary or tertiary carbon.
X X X
primary halide secondary halide tertiary halide
Note. When a halogen atom is attached directly to a C=C bond, the compounds are
commonly called vinyl halides. Benzyl and allyl halides have a CH 2 X group attached to a
benzene ring and the H 2 C=CH group, respectively.
X
X
X X
vinyl halide aryl halide benzyl halide allyl halide

127
5.2.4. Conformations of Alkanes

Conformations are different three-dimensional shapes related by rotations about single
bonds. Each conformations (or conformational isomers) can be interconverted by rotations
about single bonds.
For ethane, there are two extreme conformations:
H H bond H HH
H rotation H
H
H H H H
staggered conformation eclipsed conformation
These two conformations (rotamers) are best represented using Newman projection:
H H H HH
H H
H
view from here H H view from here H H
H
H HH
H H H
H H
H HH
Newman Projection Newman Projection
staggered conformation eclipsed conformation
5.2.5. Reactions of Alkanes

Organic reactions involve making and breaking covalent bonds. Bond scission (breaking)
depends critically on two parameters:
• Bond strength (bond energy)

• Bond polarity
C C bond energy: 346 kJ mol-1
bond polarity ∆χ = 0
very small partial charges

C H bond energy: 416 kJ mol-1
δ- δ+
bond polarity ∆χ = 0.4 C H
So alkanes are not chemically reactive, and will react only under extreme conditions.
Two important reactions of alkanes are: combustion and halogenation.

128
5.2.5.1. Combustion
The details of combustion processes are very complex and you will discuss some of what
goes on in later lecture courses. Combustion is a made of sequences of exothermic
chemical reactions between a fuel (hydrocarbon) and an oxidant (oxygen). Combustion is
accompanied by the production of heat and by the conversion of chemical species.
Example In the complete combustion reaction of a hydrocarbon with pure oxygen, CO 2 and
H 2 O are produced and heat is released.
2 CnH2n+2 + (3n+1) O2 2n CO2 + (2n+2) H2O
Note. Any combustion at high temperature in atmospheric air (which contain 78% of
nitrogen) will also generate small amounts of several nitrogen oxides (NOx)
5.2.5.2. Halogenation
Halogenation is a chemical reaction with a halogen and occurs under intense UV radiation.
Example:
Chlorination of ethane.
Cl2
CH3 CH3 CH3 CH2 Cl + HCl
intense UV radiation
ethane chloroethane
not very reactive primary alkyl chloride
now reactive and useful
Chlorination of n-butane.
Cl2
Cl + HCl
+
intense UV radiation
Cl
primary alkyl chloride secondary alkyl chloride
Let’s look closely at the secondary alkyl chloride formed. ..

129
n-butane
H H
H Cl Cl H
rotate the molecule

Mirror
H Cl Cl H
These two molecules are mirror images of each other; and are non-superimposable: they
are two enantiomers.
Enantiomers are different molecules - a type of stereoisomers: the atoms have the same
connectivity but differ in the three-dimensional orientation of some of the atoms
.
The two secondary alkyl chlorides are asymmetric, non-superimposable mirror images: they
are chiral.
Chirality derived from the Greek Χερι (“cheri”), hand. Hands are mirror images of each
other and are non-superimposable.
A molecule with a sp3 C centre with four different groups attached is chiral. If the two mirror
images are non superimposable, they are enantiomers.
Mirror
A A
D D
B B
C C
4 different groups on an sp3 C - the molecule is chiral

130
Exercise: If two of the four groups are identical:
Mirror
Cl Cl Cl Cl
not all 4 groups on the sp3 C are different - here two groups are identical-
mirror image is superimposable (same molecule).
molecule is ACHIRAL
Test yourself: are these molecules chiral?

HO H HO H
Br H Br O
chiral achiral achiral chiral
The synthesis of 2-chlorobutane on the previous page is done in a non-chiral environment,

nothing favours one enantiomer over the second one; so a 1:1 mixture of enantiomers is
obtained; the product of the reaction is a racemate (or a racemic mixture).
In a non-chiral environment, two enantiomers will have the same physical properties. But if
the surrounding environment is asymmetric (such as in the chiral environment of the
biochemistry within our bodies), they will have different properties.
Life is asymmetrical: most bio-molecules in our bodies are chiral (e.g. DNA, enzymes,
proteins):
DNA

131
All enzymes and proteins found in our bodies and in natural life forms in general are
all made of chiral amino acids building blocks. Only one of the two possible
enantiomers of amino acids is used in life forms (for example L-alanine); the other
one (D-Alanine) is not seen in biology.
mirror
H NH2 H2N H
OH HO
H3C CH3
O O
natural amino acid (L) Alanine unnatural amino acid (D) Alanine
chiral chiral
So it really DOES matter whether we use the right-handed of left-handed molecule

Our body tends to interact with each enantiomer differently because our bodies are chiral
environments.
This is important in medicines (pharmaceutical bioactivities), but also for taste, scent, etc.
mirror
O O
H H (teratogenic)
(sedative)
O O
O N O O N O
H H
(R)-Thalidonide (S)-Thalidonide
Thalidomide was first introduced in the late 1950s as a sedative; it was prescribed to
morning sickness in pregnant women. Unfortunately, thalidomide was subsequently found to
be the cause of severe birth defects in children. Over 10 000 children were born with major
malformations as a result. This was due to the fact that Thalidomide exists as two
enantiomers R and S. In human, the R enantiomer is an effective sedative, but the S
enantiomer is teratogenic (causes malformation of fetuses).
L D
Smell
mirror
smell of lemons strong smell of oranges
H H
(S)-Limonene (R)-Limonene
Me mirror
Me
Me Me
odourless H H very persistent odour
of urine and sweat
H H H H
O O

132
Taste
mirror
NH2 NH2
H H
Sweet HO2C N CO2Me MeO2C N CO2H Bitter
O O
Ph Ph
aspartame
Introduction to reaction mechanism and curly arrows
• When two molecules find themselves close together, a reaction can take place,
provided electrons move from one atom to another.
• Mechanism of a reaction is a detailed description of the pathway electrons take when
the two molecules react.
• A bond forms when electrons move from a nucleophile to an electrophile:
electron pairs movement
(2e-)
Nu E
Nu E
from nucleophile to electrophile
• The nucleophile donates electron pairs, the electrophile accepts electron pairs.
curly arrow showing electron pairs movement
Cl + H Cl H
from nucleophile to electrophile bond formed
(straight arrow is reaction)
Curly arrows always start from electron rich sources and end in electron poor places.
Nucleophiles – donate electrons – example of typical nucleophiles:
NH3 Br
a lone pair a negative charge a double bond
"electron rich" π-bond

133
Electrophiles – will accept electrons – example of typical electrophiles:
+
δ δ
-
δ+ -
δ O
H H Cl
a positive charge single bond a double bond

to an electronegative atom to an electronegative atom
Typical electrophiles are electron deficient species such as cations or atoms bonded to
electronegative atoms.
5.3. Halogenoalkanes (Alkyl Halides)
5.3.1. Structure and Reactivity

The main feature of alkyl halides is the polarized C-X bond (X = halogen).
C-X bond is polarised, resulting in a partial charge on C
H H electronegativity of C: χ = 2.55
δ+
C δ- electronegativity of halogen: F: χ = 3.98
H3C X Cl: χ = 3.16
Br: χ = 2.96
I: χ = 2.66
H H The difference of electronegativity between two atoms

bonded by σ-bond results in an inductive effect.
C
H3C X The two electrons forming the bond are not shared equally
but are attracted towards the more electronegative atom.
inductive effect
The inductive effect is represented as an arrow along the polarized bond directed towards
the more electronegative atoms.
Halide anion X- is stable (e.g. F-, Cl-, Br- can all exist as anionic species in solution) so the
chemistry of alkyl halides is dominated by the breaking of a C-X bond in this way:
H H
C
H3C X
alkyl halide
Due to the inductive effect on the C-X bond, the carbon centre (C-X) of alkyl halide is
electron deficient: it is an electrophile. Electrophiles can be attacked by nucleophiles.

134
5.3.2. Substitution Reactions SN2 and SN1.

There are two major classes of nucleophilic substitution reactions on alkyl halides:
bi-molecular S N 2 or uni-molecular S N 1.
S N 2 Reaction
• The S N 2 reaction only happens because a nucleophile attacks the electron deficient
carbon. As a result of this attack, and simultaneously; a halide anion separates.
• The speed of an S N 2 reaction depends on the concentration of the two species
(nucleophile and the alkyl halide). S N 2 is a bi-molecular or concerted reaction.
• All bond breaking and bond making occurs simultaneously.
H H H
SN2 H
C C +X
H3C X Nu CH3
Nu alkyl halide
S N 1 Reaction
• The reaction occurs because a halide anion separates first, leaving an electron
deficient carbocation (which is a strong electrophile).
• The speed of an S N 1 reaction depends on the concentration of the alkyl halide only.
H3C CH3 H3C CH3 H3C

SN1 CH3
C C +X C +X
H3C X Nu CH3
CH3
alkyl halide
Nu

135
S N 2 Reaction profile:
Energy
[transition state]
S N2
energy barrier =
activation energy
starting materials
products
Reaction progress
H H
H H
H H
C δ- δ+ -
δ C +X
H3C X Nu X
Nu Nu CH3
CH3
starting materials [transition state] products
All bonds breaking and bond making occurs simultaneously during the transition state. The
lower the energy barrier at the transition state, the faster the reaction.
Notes.
• The S N 2 reaction will be faster with a strong nucleophile. (e.g. OH-, RO-, CN- from
NaOH or KOH ; NaOR ; NaCN or KCN respectively).
• The leaving group X can be Cl, Br, I (all good leaving groups).
Example of S N 2 reactions
H H
H H
C δ- δ+ H H
+ δ-
H3C δ Br HO Br
+
Na OH C Na+ + Br
δ-
HO CH3
CH3
nucleophile
δ+ [transition state] products
electrophile (C )

136
S N 2 proceeds via a 5-coordinate transition state.

• The nucleophile operates a rearside attack of the carbon centre; behind the C-Br
bond.
• The carbon go via a 5-coodinate transition state: dotted line denotes partial bond
breaking and forming simultaneously.
More examples of S N 2 using different nucleophiles and alkyl halides:

sodium ethoxide (NaOEt)
H H H H
C C Na+ + Br
+ S N2
n-Pr δ Br EtO n-Pr
+
Na EtO δ-
products
nucleophile
sodium cyanide (NaCN)
H Et H Et
C C Na
+
+ S N2 + Br
Me δ Br C Me
Na+ N C δ- N
nucleophile products
rearside attack Inversion of the carbon stereochemistry
Note. The inversion of stereochemistry of the carbon centre. The inversion of

stereochemistry is explained by the concerted transition state:
H Et
δ- δ+ δ-
N C Br
Me
[transition state]
Relative rates of reaction: S N 2 reactions are faster on the less substituted carbon centre.
H H H H H CH3 H3C CH3
C C C C
H X H3C X H3C X H3C X
primary alkyl halide secondary tertiary
Faster rate of SN2 Does not undergoe SN2

137
This is explained by the necessity of a rearside attack on the carbon centre by the
nucleophile: when the carbon centre is more accessible, the reaction is faster.
Comparing the two extremes:

H
H H
H H H C
X H HC
H
C C
Nu C X
H X H
Nu H Does not undergoe SN2
easy access, lots of space too much obstruction

no space for rearside approach STERIC HINDRANCE
It is also the reason why S N 2 only works on sp3 carbon centres. S N 2 reactions on sp2 or
sp carbon centres are not possible:
X XR C X
C X
Nu Nu
no rearside attack possible no rearside attack possible
Due to steric hindrance, tertiary alkyl halides cannot undergo S N 2 reaction; and will react via
a different mechanism : a S N 1 reaction (nucleophile substitution –uni-molecular).

138
S N 1 Reaction profile:
Energy
step 1
S N1
step 2
small energy barrier (fast step)
activation energy of step 2
energy barrier = carbocation
activation energy intermediate
starting materials
products
Reaction progress
H3C CH3 H3C CH3 H3C

step 1 step 2 CH3
C C +X C +X
SLOW fast
H3C X Nu CH3
CH3
alkyl halide Nu carbocation intermediate products
planar sp2 hybridised
less congested
Now can be attacked by a nucleophile
The first step is slow (high energy barrier) and determines the speed of the reaction (first
step is rate determining).
• The rate of reaction is limited by this first step which depends on the alkyl halide only.
• The strength or the concentration of the nucleophile will not affect this first step; the
reaction speed only depends on the alkyl halide. (S N 1 is uni-molecular).
• It makes no difference to the rate if the reaction uses H 2 O (poor nucleophile) or OH-
(much better nucleophile)

139
Example of S N 1 reaction:
H3C CH3 H3C CH3 H3C

step1 CH3
step2
C C +X H C
SLOW fast
H3C Cl O CH3
H CH3
alkyl halide
O H
carbocation
intermediate solvent or X
H
very fast
-H+ deprotonation step
H3C CH3
H C
+ HX
O CH3
products
Relative rates of reaction: S N 1 reactions are faster on more substituted carbon centres.
can undergo SN1

Do not undergoe SN1
H H H CH3 H3C CH3

H H
C C C
C
H3C X H3C X H3C X
H X
Faster rate of SN1

S N 1 reaction proceeds via a carbocation intermediate: the carbocation has to be stable
enough to stay in solution until the nucleophile is able to attack. The more stable the
carbocation the faster the reaction.
inductive effect more inductive effect
H H H3C H H3C CH3 H3C CH3

C C C C
H H H CH3
not stable primary carbocation tertiary carbocation

carbocation very unstable most stable
Alkyl groups have a slight inductive effect, donating electron density that stabilises the
carbocation.

140
Stereochemistry of S N 1 versus S N 2.
• S N 2 gives inversion of stereochemistry (see page 22).

This is due to the concerted, rear side nucleophile attack during the transition state.
• S N 1 gives a racemic product if the starting material is an enantiopure alkyl halide.
This is because the intermediate carbocation is planar.

Nucleophile can therefore attack equally from either side of the carbocation.
empty p-orbital
Bu Et Bu Et carbocation intermediate
step 1
C +X planar sp2 hybridised
H3C X SLOW
CH3
sp3 hybridised C Nu Nu
nucleophiles can approach from either side
step 2 fast
Bu Et Et Bu
C C +X
Nu CH3 H3C Nu
products: 1:1 enantiomeric mixture: RACEMIC MIXTURE

141
Summary S N 1 versus S N 2 Reactivity
Faster rate of SN2, less hindrance at carbon centre Does not undergoe SN2
H H H H H CH3 H3C CH3
C C C C
H X H3C X H3C X H3C X
Do not undergoe SN1 can undergo SN1
increasing carbocation stability Faster rate of SN1
Remember the names do not refer to the number of steps but to the reaction kinetics and the
number of components involved in the rate determining step (RDS):
• S N 2 is bimolecular (one step involving two molecules).
• S N 1 is unimolecular (two steps, the first step is the RDS involving one molecule only).
5.3.3. Elimination Reactions of Alkyl Halides E2 and E1.

In the previous chapter we have seen that tertiary alkyl chlorides give alcohols by S N 1
nucleophilic substitution. In fact there is a competing reaction: elimination reaction E1.
Elimination E1 is uni-molecular (in two steps via a carbocation).
H3C CH3 SN1

step2
C +X alcohol
fast
CH3 H
O
H3C CH3 nucleophile
C H
OR
SLOW
H3C Cl
H3C CH3 E1
H3C CH3
step2
C +X C
fast
H2C CH2
H H
O
base
H
If the carbocation intermediate is attacked by a nucleophile, we have a S N 1 reaction. If a
proton at one of the α-carbons with respect to the carbocation is removed by a base; we
have an E1 elimination reaction.

142
The overall E1 elimination reaction gives alkene:
H3C CH3
Elimination H3C CH3
C C
H2C Cl -HCl
CH2
H
alkene
E1 Reaction profile:
Energy
step 1
E1
step 2
small energy barrier (fast step)
activation energy of step 2
energy barrier = carbocation
activation energy intermediate
starting materials
products
Reaction progress
As S N 1 and E1 pathways compete, the product of the reactions is often a mixture of the
S N 1product (alcohol) and the E1 product (alkene).
H3C CH3 H3C CH3

H 2O H3C CH3
C C C +X
H3C X Heat HO CH2
CH2
alkyl halide SN1 products E1 products
MAJOR Minor

143
If the substituents are not all identical on the tertiary alkyl chloride; then more than one
alkene can be obtained by the E1 pathway.
H2
H3C CH3 H3C C
H 2O H H3C CH2
C C C
H2C X SLOW
-X CH H2C
CH3 H CH3 CH3
disubstituted alkene
alkyl halide
Minor E1 product
H3C CH3
C
The major E1 product is the
more substituted alkene
HC
CH3
tri-substituted alkene
MAJOR E1 product
Comparing H 2 O with NaOH as nucleophile and as base:
OH- H2O
Nucleophilic character STRONGER Weaker
Basic character STRONGER weaker
If we change the reaction conditions: replacing H 2 O by OH- (a stronger base): a different

reaction occurs:
• OH- does not wait for C-X to break to form the carbocation.
• OH- can directly attacks to remove a hydrogen, resulting in the C-X bond to break
simultaneously.
With a stronger base, (OH- is acting as a base rather than a nucleophile: it removes a
hydrogen).

144
E2 Reaction profile:
Energy
[transition state]
E2
energy barrier =
activation energy
starting materials
products
Reaction progress
strong base
H3C CH3
OH H3C
H3C CH3 CH3 C
H C δ- H C δ-
SLOW CH2
C Cl HO C Cl
H2 H + H2O + Cl-
[transition state]
starting materials products
E2 reaction is a bimolecular reaction: the speed of reaction depends on the concentration of

both: base and alkyl halide.
E2 reaction proceeds in one step via a transition state, where bonds form and break
simultaneously - dotted line denotes partial bond breaking and forming.
E2 stereochemistry is anti-periplanar.
In the transition state: C-H and C-Cl bonds are positioned in the same plane and are at 180o
(anti) to each other.
Newman Projection
HO
H3C CH3 H
HO H C H3C CH3
C Cl
H H H H
view
Cl
anti periplanar anti periplanar

145
Table. Summary E1 versus E2 Eliminations.

Alkyl Halide E1 E2
Primary No, carbocation too unstable E2 favoured
Secondary E1 main reaction with E2 main reaction with
Tertiary weak bases (H 2 O, ROH) strong bases (OH-, RO-)
5.4. Alkenes
Alkenes are an important class of organic compounds that contain a C=C bond. Alkenes are
useful compounds in organic synthesis because the C=C bond reacts with a large number of
electrophiles in electrophilic addition reactions.
5.4.1. Structures and Reactivity

The C=C bond of an alkene contains one strong σ bond and one weaker π bond.
Example of alkene: ethene
π-bond
P P
H H H H
2 C C C C
sp
H H H H
Unhybridised p-orbital on each C
The double bond is formed by overlap of the orbitals on the two sp2 hybridised carbons. One
sigma bond is formed by “end-on” overlap of sp2 orbital of one carbon with an sp2 orbital of
the second carbon. The p bond is formed by “side-on” overlap of the unhybridised p orbitals.
• alkene’s C is sp2 hybridised

• each C has a trigonal planar geometry
• all atoms bonded to C are in the same plane
Table. Comparison C=C with C-C and C≡C.

Bond hybridization- geometry bond lengths (pm) bond enthalpies (kJ mol-1)
C-C sp3 – tetrahedral 153 (longest) +347 (weakest)
2
C=C sp – trigonal planar 134 +612
C≡C sp - linear 120 (shortest) +838 (strongest)

146
Relative stability and reactivity of C=C bonds.

The double bond is rigid; no rotation around C=C bond is possible without breaking the
π bond. As a result, a C=C bond in the middle of a carbon chain can have different
configurational isomers: cis- and trans-isomers.
steric strain
Me H Me Me
H Me H H
trans-but-2-ene cis-but-2-ene
trans more stable cis less stable
The more stable of the two configurational isomers is the one with the two largest
substituents on the opposite sides of the C=C bond - because this minimises steric strain.
Note. cis/trans nomenclature of alkenes: The cis/trans system works by assigning relative
priorities to the two substituents on each carbon of the double bond. The relative priorities
are determined by the mass of the atom directly attached to each carbon atom in the double
bond in order of decreasing atomic number (the heaviest atom has the highest priority).
Configurational stereoisomers
Cis and trans isomers are configurational stereoisomers; they share the same molecular
formula and the same structure but the positions of the atoms in space are different. There
are two types of configurational isomers, cis- trans-isomers and isomers with chiral centres.
Stereoisomers
configurational isomers
conformational isomers cis- and trans-isomers isomers with chiral centres
H
H CH3 H HCH
H 3 H3C H3C
Me Me
and and and
H H H H
CH3 H3C Pr Et
Et Pr
H HH
staggered eclipsed trans-isomer cis-isomer
conformation conformation

147
The stability of alkenes is influenced by the electronic effects of the substituents attached to
the C=C bonds. The more substituted the C=C bond; the more stable the alkene.
R2 R2
R3 R3 > R2 R2
R1 >R R1 > R ; > R1
1 1
R4 R2 R1
tetrasubstituted > trisubstituted > trans-disubstituted > cis-disubstituted > monosubstituted
terminal-disubstituted
5.4.2. Synthesis of Alkenes

Alkenes are commonly prepared by elimination reactions starting from either
halogenoalkanes (by base-induced E2 reaction) or from alcohols (by acid-catalysed E1
reaction).
5.4.2.1. By Base-Induced Elimination from Alkyl Halides (E2).
α (base)
H -
EtO NaOEt EtOH + Br
β Br
EtOH
(solvent)
Note. If more than one alkene can be obtained; the more substituted alkene (more stable) is
usually the major product. [Zaitsev’s rule].
Br
NaOMe
α
MeOH
major (74%) minor (26%)
H H
β β
choice!

148
5.4.2.2. By Acid-Catalysed Elimination of Water from Alcohol (Dehydration of Alcohols) (E1)
Alcohols can be dehydrated in strong acids to give alkenes, via a carbocation intermediate
(E1 reaction). This happen when using reagents that convert the OH group of the alcohol
into a compound that provides a good leaving group.
OH H+
H2SO4, H2O
H H
O
H + H2O
α
β
carbocation
• Strong acid used: sulfuric acid (H 2 SO 4 ) or phosphoric acid (H 3 PO 4 )

• Must not use acids which can produce strong nucleophiles (e.g. not HCl) to avoid
competition between substitution (S N 1) and the desired elimination (E1).
Note. If more than one alkene can be obtained, - the more substituted alkene (more stable)
is usually the major product. [Zaitsev’s rule].
more substituted
alkene
+
OH H +
H2SO4, H2O
major minor
Hβ
H H α
O + H2O
βH
choice!
The reaction proceeds via a carbocation intermediate; if there is a choice; the

reaction will go via the more stable carbocation.

149
Stability of carbocations (R = alkyl group)
inductive effect more inductive effect
R H R1 R2 R1 R2
C C C
H H R3
primary carbocation tertiary carbocation

very unstable most stable
Summary ease of E1 reaction:

Best for E1 reaction
H H H R2 R3 R2
C C C
R OH R1 OH R1 OH
primary alcohol secondary alcohol tertiary alcohol
Does not undergoe E1 can undergo E1
increasing carbocation stability ease of E1 reaction
5.4.3. Reactions of Alkenes

The carbon atoms in the C=C bond are held together by four electrons, so this bond is
electron rich and acts as a nucleophile in reactions. The reactions of nucleophilic C=C bonds
with electrophiles, E+, are called electrophilic additions because the first step of the reaction
involves addition of the electrophile to the multiple bond.
E
electrophile
"electron rich" π-bond

nucleophile
The carbocation that is formed then reacts with a nucleophile, Nu-. As a result, the double
bond gives rise to two single bonds.

150
5.4.3.1. Addition Reactions

a) Addition of H-X across the double bond
R1 R2 R1 R2
H-X
C C H C C X
R4 R3 R4 R3
Example of Mechanism:
Me H Me H
H-Br H
C C
Br
H Me H Me
δ+ H
carbocation
δ- Br Me H
H C C Br
H Me
If the alkene is not symmetrical then two possible products can be obtained, depending on
which end of the alkene the first proton will be bonded.
H Me H Me Cl Me
H-Cl H H
or
H Me H Me H Me
Cl H
A B
MAJOR
The major product goes via the more stable carbocation intermediate [Markovnikov rule].
H Me H Me
H A
Cl MAJOR
H Me H Me
H
tertiary carbocation
Cl (more stable)
H Me H Me
B
H Me H H
Me
H Cl
Cl primary carbocation
(NOT stable)
Note. Students must be able to explain the regiochemistry of a reaction, showing the most
stable cation intermediate.

151
.
b) Addition of water to give alcohol (hydration of alkene).
H Me H2SO4, H2O H Me OH Me
H H
H Me Me
H Me OH H H
this other isomer is not formed
(carbocation stability)
Mechanism:
H Me Slow H Me H Me + H Me
H H -H H
Me Me
H Me H Me O H H
O H H OH
H H
H
tertiary carbocation preferred
O
H H (or H+)
This process is the reverse of the acid-catalysed dehydration of alcohols to give alkenes.
Such interconversion is reversible:
Forward: Remove water/distill off alkene
H Me acid catalyst H Me
H
+ H2O
H Me
OH H Me
Backward: Increase pressure (Le Chatelier's principle)
c) Addition of Halogens (Cl 2 , Br 2 ).

Example:
H Me Br Me
Br2 H
Me H Me H
Br
Mechanism:
Br δ− Bromonium Ion
Br δ+
Br SN2 Br Me
H Me H Me H
Me H Me H H
Me Br
Bromine molecule
Br
polarises when
approaches the
alkene π-bond

152
Stereochemistry: trans-addition.
Br2 Br SN 2
H H inversion H Br
Br Br H
trans addition
Bromonium Ion
5.4.3.2. Reduction of Alkenes (to give alkanes)

By direct addition of hydrogen gas (H 2 ). The reaction needs a catalyst.
Catalyst such as palladium metal deposited on charcoal (Pd/C) is used.
R1 R2 H2, Pd/C R1 R2
R4 R3
R4 R3 H H
Mechanism: a surface process.
HH R1 R2 R1 R2
+ alkene
R4 R3 R4 R
HH H H H H 3
Pd surface Pd surface cis addition
Addition of hydrogen via Pd/C catalyst is a surface process leading to a cis-addition – both
atoms add to the same face of the alkene.
H
Me Me
H2, Pd/C cis
(same face)
Me Me
H
cis addition
5.5. Alcohols
All alcohols contain the hydroxyl (-OH) group and have the general formula ROH.
5.5.1. Structure, Properties, and Acid-Base Reactions
5.5.1.1. Structure and Properties
Alcohols are classified as primary, secondary, or tertiary alcohols in the same way as
halogenoalkanes. The classification depends on whether the OH group is bonded to a
carbon atom bearing one, two, or three alkyl groups.
R2 R2
CH3OH R1 OH R1 OH
R OH R3
methanol primary alcohol secondary alcohol tertiary alcohol
Examples:

153
primary secondary tertiary
OH OH OH OH
OH
Ethanol i-Butanol n-Butanol i-Propanol t-Butanol

(ethyl alcohol) (butan-1-ol) (propan-2-ol) (2-methylpropan-2-ol)
Polarisation of the OH group. Oxygen atom is more electronegative than C and H, so C-O
and O-H bonds are both polarized, with a negative partial charge on O.
δ+
H H
electronegativity (c) -
O O δ
H: 2.1 δ+C
C: 2.5 C
O: 3.5
C-O and O-H bonds are POLARISED
Simple alcohols are polar solvents, much less volatile than alkenes or alkanes of similar
molar masses.
Shape of the alcohols (R-OH) : oxygen is sp3 hybridised – it has two lone pairs of electrons.
The C-O-H unit is bent.
H
O
R
C-O-H unit is bent
There is extensive hydrogen bonding in a liquid alcohol (like in water). This means that
alcohol’s Hs exchange from one molecule to another very rapidly.
H
H O
R O H O
R
R
H
R O H O
R
H bondings

154
Alcohol molecules are neutral - like water they can be either deprotonated (by a strong base)
or protonated (by a strong acid).
pKa of alcohol in water:
H H
O CH3 O + H O
H O
+
H3C H H
- +
Ka = [CH3O ][H3O ] pKa = -log10 Ka
[CH3OH] pKa MeOH = 15.5
-16
= 3.2 x 10
Comparison of acidity:
neutral
OH
O
R OH H2O
HCl R OH (R=alkyl)
carboxylic phenol alcohol water
acid
pKa -7 ~5 ~ 10 ~ 15 15.7
more acidic
5.5.1.2. Reactions with Acids and Bases.
H+ H
R OH R O
OH- is a very poor Much better

leaving group leaving group!
(H2O)

155
Mechanism; protonation of the alcohol followed by a E1 (via carbocation):
OH H+
H2SO4, H2O
OH- is a very poor
leaving group
H
H H β
Much better O + H2O
α
leaving group!
(H2O)
carbocation
Protonation of alcohols to generate a good leaving group (H 2 O) can also be followed by a

S N 1 and S N 2 reactions.
Example, S N 1: synthesis of alkyl halides using HCl, HBr or HI from a tertiary alcohol.
H+ Cl
OH
OH- is a very poor HCl
leaving group so
cannot do SN1
directly on alcohol
H+
H H
Much better O Cl-
leaving group!
S N1
(H2O) Now can
undergo SN1
carbocation
Or with a primary alcohol (S N 2):
-
HCl Cl H
H+ SN 2
OH O Cl
fast slow
H
OH- is a very poor Much better

leaving group so leaving group!
cannot do SN2 (H2O) Now can
undergo SN2
directly on alcohol

156
• Strong bases such as (NaH or KH) can deprotonate an alcohol to give an alkoxide
anion:
+ - + -
Na H H OR Na OR + H2 (gas)
Note. You cannot use sodium hydroxide (NaOH) to deprotonate alcohols as it is not a strong
enough base. You need sodium hydride (NaH) or potassium hydride (KH).
The product, NaOR, is called sodium alkoxide. For example, sodium methoxide (NaOMe),
and sodium ethoxide (NaOEt) can be made this way.
Another way to make an alkoxide from simple alcohol is to oxidise sodium metal in the
alcohol:
-
2 ROH + 2 Na 2 Na+ 2 OR + H2 (gas)
• Alkoxides (RO-) can behave as both nucleophiles and bases.
For example, they can be nucleophilic with primary alkyl halides leading to a S N 2.
NUCLEOPHILE
NaH Br
+ NaBr
OH O- Na+ O
SN2
primary alcohol alkoxide ether
Note. This is in fact a general method for forming ethers, called Williamson Ether
Synthesis.
For general reaction:
NaH R'X O
ROH Na+ OR- R R'
(X=halogen)
ether

157
But with tertiary alkyl halides (which are too hindered to do a S N 2), they act as a base,
leading to elimination E2.
OEt Na
BASE
H E2
+ NaBr + EtOH
Br
tertiary alkyl halide
For secondary alkyl halides, see summary bellow:
Table. Reactions of alkoxides with alkyl halides.

Alkyl Halide primary secondary tertiary
Alkoxide acts as a nucleophile both base
Reaction is SN2 S N 2 (Major) and E2 E2
The steric hindrance of the alkoxide itself can also determine whether it prefers to act
as either a nucleophile or a base:
primary alkoxide
nucleophile O
SN2 O
C6H13 Br C6H13
Tertiary alkoxides are so hindered that they are a lot less nucleophilic and so tend to
act as bases.
tertiary alkoxide BASE
H E2
C6H13
C6H13 Br

158
However, in absence ofa β-H available for elimination, tertiary alkoxide can still act
as nucleophile.
tertiary alkoxide
nucleophile CH3
CH3
CH3
O CH3 CH3
H SN2
O CH3
H H
α
I CH3

159
5.5.2. Synthesis of Alcohols

5.5.2.1. From Alkyl Halides by Nucleophile Substitution with Hydroxide Ion.
• This method works best with primary alkyl halides:
Na+ SN2
Br OH
+ NaBr
-
OH
• This method is okay, but less satisfactory with secondary alkyl halides because the
elimination reaction E2 also occurs (with nucleophile acting also as base).
• This method cannot be used on tertiary alkyl halides because the steric hindrance
makes a S N 2 impossible and E2 will take place instead.
• For tertiary alkyl halides, using neutral H 2 O as nucleophile, the reaction goes via a
S N 1. But the reaction is not so attractive because H 2 O is also a base and E1
products also form; a mixture of S N 1 and E1 products is obtained. (see 5.3.3.)
5.5.2.2. From Alkenes by Acid-Catalysed Addition of Water
H Me H Me
H2SO4, H2O H
Me
H Me H OH
+
H
H H Me
Me
H H
H
O
Me
H H O
Me H H
tertiary carbocation preferred H
The reaction goes via the most stable carbocation; it is a “Markovnikov addition”

160
5.5.2.3. From Aldehydes or Ketones by Reduction:
The reduction of an aldehyde or ketone needs the use of a hydride (H-) as nucleophile to
attack the carbon of the carbonyl group (C=O).
O reduction OH
H
reagent?
R R' R R'
ketone
(R and R' = alkyl or aryl) alcohol
aldehyde
(R = alkyl or aryl or H; R' = H)
NaH does not work very well because the reagent is too basic and will deprotonate the
alcohol (see 5.5.1.2).
The reduction is best done using sodium borohydride (NaBH 4 ). In which case NaBH 4 is used
in alcoholic solution (usually with ethanol as solvent).
reducing agent
O OH
NaBH4 H
Ethanol
R R' R R'
ketone or aldehyde solvent alcohol
NaBH 4 : Remember that there is no lone pair on B. The negative charge is a formal charge
and is not really on B but is spread across all the B-H σ-bonds. Therefore, a nucleophilic
attack must start from where the electrons actually are:
H H
H H
X H H
+
+ E
Na B E Na B
Na B
H H H H
H H
sodium borohydride no lone pair on B ! arrow should start
the arrow must not start from B where electrons are

161
Mechanism:
δ−
O
O H OEt OH
H H H H
R δ+ R'
B
H H R R' R R'
Examples:
O NaBH4 OH
H EtOH H
H
aldehyde primary alcohol
O NaBH4 OH
EtOH
H
ketone secondary alcohol
Exercises - if we want to make the following alcohols from reduction; what are the starting
materials we should start with?
OH O
NaBH4
EtOH
OH NaBH4 O
EtOH

162
5.5.3. Oxidation of Alcohols

Primary and secondary alcohols can be oxidized easily, but tertiary alcohols are resistant to
oxidation:
OH O
oxidation
R H -2H R H
H
primary alcohol aldehyde
OH O
oxidation
R R' -2H R R'
H ketone
secondary alcohol
OH
R
R''
R' X cannot oxidise!
tertiary alcohol
Oxidising reagents commonly used:
Chromium in (VI) oxidation state, such as:
O O 2K O
HO VI OH
VI VI O VI
Cr Cr Cr Cr
O O O O O O
O O
chromium trioxide chromic acid potassium dichromate

CrO3 K2Cr2O7
The oxidation reactions are done in acidic solution: Jones’ reagent is commonly used - it is
a solution of chromic acid [mixture of chromium trioxide in dilute sulfuric acid (CrO 3 in
H 2 SO 4 /H 2 O)].
Secondary alcohols are oxidized well using Jones’ reagent:

OH O
CrO3
H2SO4, H2O
OH O
CrO3
H2SO4, H2O
secondary alcohol ketone

163
For primary alcohol: there is a complication.
OH O O
oxidation can further
R H -2H R H oxidise! R OH
H
primary alcohol aldehyde carboxylic
acid
With Jones’ Reagent, which are done in acidic conditions, the oxidation tends to go all the
way to carboxylic acid.
Example:
OH
CrO3
OH O
H2SO4, H2O
primary alcohol carboxylic acid
If we want to obtain the aldehyde: a milder oxidizing reagent must be use; for example
pyridinium chlorochromate (PCC).
H
PCC
OH O
primary alcohol aldehyde
O Cr Cl
N O
H
Pyridinium chlorochromate (PCC)

164
Summary: Oxidation and reduction of alcohols:
OH O O
PCC Jones' Reagent
R H R H R OH
H
primary alcohol aldehyde carboxylic
NaBH4 acid
reduction
OH Jones' Reagent O
or PCC
R H R R'
R'
secondary alcohol ketone
NaBH4
reduction
OH
cannot be oxidised
R R'' cannot be made from reduction
R'
tertiary alcohol

165
5.5.4 Grignard Reagents

5.5.4.1. The carbonyl group.
p p
δ-
O O
R2
O C
R1 R
1 R2 R1 δ+ R2
• Carbon and oxygen atoms of the C=O are both sp2 hybridised; the group is planar,
• The O lone pairs are in the plane of the molecule.
• Both the σ and the π bonds in C=O are polarised towards the more electronegative
O.
• The carbon has a positive partial charge and is electrophilic.
The typical way aldehydes or ketones react with nucleophiles:
O O OH
H+
work up
R R' R R' R R'
Nu
Nu Nu
5.5.4.2. Grignard Reagents.

Grignard Reagents (RMgBr) are very useful nucleophile for reaction with carbonyls
• R can be an alkyl, alkene, alkyne or aromatic

• a Grignard reagent is a source of carbon centred nucleophile R-.
Note. Alternative Grignards such as RMgCl or RMgI are also used, and all work the same
way.

166
Why is RMgBr a source of the nucleophile R-? (looking at the case of n-BuMgBr):
δ+
MgBr
δ-
• Mg is less electronegative than C so
• C-Mg is polarised towards the C
• C has a partial negative charge
It reacts as a nucleophile: n-Bu-.
+
MgBr
nucleophile
n-Bu-
Note. Do not confuse with alkyl bromide (C has a partial positive charge is an electrophile)
δ-
Br
δ+
alkyl bromide - partial positive charge on C
Reactions of Grignard Reagents with Aldehydes and Ketones
O BrMg O H+ OH
work up
R R' Me MgBr R R' R R'
Me Me
When reaction complete,

add aq. acid (H+/H2O),
this is called "work up"
Note. Grignard reagent (RMgBr) can be represented in its ionic extreme form as R- + BrMg+
(to help remembering about its reactivity).
Altenatively the full formula can be drawn and the mechanism is represented by the arrow
starting from the covalent bond Me-MgBr.
O BrMg O H+ OH
δ− δ+ work up
R R' Me MgBr R R' R R'
Me Me

167
Examples:
Grignard Reagent with an aldehyde:
O BrMg O OH
H+
δ− δ+ work up
H Et MgBr H H
Et Et
Grignard Reagent with a ketone:
δ− δ+ O
MgBr OH
O BrMg H
+
Dry ether aq. work up

(ether = Et2O,
Source of: is a solvent)
δ− δ+ O
O MgBr OH
BrMg H+
But Me But Me
But Me
Dry ether aq. work up
Source of:

168
How to make Grignard Reagents
From reacting alkyl halide with Mg in dry ether
Mg
R X R MgX
Dry ether
alkyl halide Grignard
(with X=Cl, Br, I)
Examples:
Mg
Br MgBr
Dry ether
Grignard
Br MgBr
Mg
Dry ether
Grignard
Mg
Br MgBr
Dry ether
Grignard
Note. Grignard reactions need to be done in dry conditions because Grignard Reagents can
react with water, and won't be reactive anymore!
O
Ph MgBr H H PhH
not useful as reagent!
Note. Grignard reagents will be examined further in semester 2.

GLOSSARY
Glossary
Absorption spectra
When the sun light is first filtered through a tube containing atoms of gases, some
wavelengths are selectively absorbed by the atoms, leaving dark lines known as
absorption lines in the spectrum.
Acid/base reactions.
Because an acid can be defined either as a proton donor or as an electron acceptor;
there are two definitions of acid/base reaction.
According to the Brǿnsted-Lowry definition an acid is a donor of proton (H+) and a
base is an acceptor of proton. Acid/base reaction thus is an exchange of proton.
According to the Lewis definition an acid is an acceptor of an electron pair and a
base is a donor of an electron pair. An acid/base reaction thus is an exchange of an
electron pair where a Lewis base donates an electron pair to a Lewis acid to form a
Lewis adduct by covalent bond formation.
Aufbau principle
The Aufbau principle (from the German Aufbau: “construction, building up”) is used to
determine the electronic configuration of an atom molecule or ion in its ground state
(i.e. in its lowest possible energy). This principle guides the process by which the
electronic structure of an atom is built by progressively adding electrons with each
successive electron filling an available orbital of the lowest possible energy.
Atomic radius
The atomic radius is defined as the distance between the nucleus and the boundary
of the outermost occupied atomic orbital.
Balmer series
The emission spectrum of the hydrogen atom is divided into spectral series according
to the energy level to which the electrons move down. The Balmer series is due to
electrons from higher energy levels (n = 6, 5, 4, 3) moving to the level n = 2; the
wavelengths of the emission associated with these transitions are within the region of
visible light.
Bond energy
The bond energy is the energy required to break up the bond. It is always positive.
When a bond is made; energy is released (exothermic).
Bond order
Bond order (bo) is the number of chemical bonds between two atoms.

GLOSSARY
Chirality
Chirality derived from the Greek Χερι (“cheri”), hand. Hands are mirror images of
each other and are non-superimposable. A molecule with a sp3 C centre with four
different groups attached is chiral.
Conformation
Conformations are different three-dimensional shapes related by rotations about
single bonds. Each conformations (or conformational isomers) can be interconverted
by rotations about single bonds.
Co-ordinate covalent bond

This is also known as a dipolar bond or a dative covalent bond. It is a covalent bond
in which the two electrons of the bond are provided by the same atom.
Core electrons
Core electrons occupy the inner orbitals and are not generally available for bonding.
Core electrons are responsible for the shielding effect.
Core shells
The core shells are fully filled by the core electrons. Core electrons do not generally
take part in chemical reactivity. When writing electron configurations, the core
electrons are replaced with the name of the noble gas in brackets that has the same
configuration.
Covalent bonding
A covalent bond is formed when two electrons are shared between two atoms,
generally allowing each of them to have the electronic configuration of a noble gas.
Electron affinity
Electron affinity is the energy obtained when an electron is added to an atom in the
gas phase.
Electronegativity
Electronegativity is the ability of an atom in a molecule to attract bonding electrons.
It is measured on Pauli scale (χfrom 0.7 to 4.0).
Electronic configuration
The electronic configuration describes the distribution of electrons around the
nucleus in shells and sub-shells.
Element
An element X is characterised by a number of protons Z (the atomic number) and
identified by its chemical symbol X. One element can have several isotopes.
Emission spectra
When the atoms of gases contained in a tube are heated they glow, the atoms emit
light at certain wavelengths, showing colored lines known as emission lines in the
spectrum.

GLOSSARY
Empirical Formulae
Empirical formula indicates the ratio of each type of atom in a chemical compound. It
does not give any information on structure. The formula is called empirical because it
is measured by experiment. When an unknown compound is analysed by elemental
analysis; it is combusted and the products of its combustion (e.g. CO 2 , H 2 O, N 2 ,
SO 2 ) are measured. The result of an elemental analysis is presented as a
percentage (%) by mass of C, H, N and S. A percentage (%) is expressed in gram
per 100 gram.
Enantiomers
Two molecules, mirror images of each other and non-superimposable are two
enantiomers.
First ionisation energy

The first ionisation energy E i1 is the energy necessary to remove one electron from
the outermost occupied orbital
Geometry (molecule)
The geometry of a molecule is the three-dimensional arrangement of the molecule’s
valence electrons (bond pairs, lone pairs and unpaired electrons). The molecular
geometry determines many of the substance’s properties such as chemical reactivity,
polarity, colour or magnetism.
Greek alphabet
Α, α alpha Η, η eta Ν,ν nu Τ, τ tau

Β, β beta Θ, θ theta Ξ, ξ xi Υ, υ upsilon
Γ, γ gamma Ι, Ι iota Ο, ο omicron φ, φ phi
∆, δ delta Κ, κ kappa Π, π pi Χ, χ chi
Ε, ε epsilon Λ, λ lambda Ρ, ρ rho Ψ, ψ psi
Ζ, ζ zeta Μ, µ mu Σ, σ sigma Ω, ω omega
Hund’s rule
For degenerate atomic orbitals, the ground-state electronic configuration is that with
the greatest number of parallel spins.
Hybrid orbital
Atomic hybrid orbitals are the result of mixing atomic orbitals (s, p, d, etc) from the
same atom and have their own shape and energy. Hybrid orbitals are very useful in
explaining molecular geometry and bonding properties.
Hydrogen bonding

GLOSSARY
Hydrogen bonding is a strong electrostatic interaction that occurs between the

positively charged hydrogens and negatively charged atoms (N, O, F, Cl) within the
same molecule (intramolecular bonding) or between two molecules (intermolecular
bonding).
Hypervalence
A hypervalent molecule contains one or more main group elements formally bearing
more than eight electrons in their valence shells.
Inert pair effects

The inert pair effect is a tendency of the s valence electrons to remain as a lone pair
in compounds of post-transition metals.
Ionic bonding
The ionic bond is a chemical bond formed through electrostatic attraction between a
cation and an anion.
Ionisation energy
Is the energy required to remove an electron from the atom (E i = lE ao l). The greater
the attraction with the nucleus the greater the E i of an electron.
Isotopes
Isotopes of the same element have the same number of protons Z therefore share
the same chemical symbol X, but have a different number of neutrons (a different
mass number A).
Quantum number
Solving the Schrödinger wave equation gives a set of quantised orbitals
(wavefunctions ψ) each characterized by its energy and by 3 quantum numbers:
principal (n), azimutal or angular (l) and magnetic (m l ).
Law of mass conservation

The law of mass conservation implies that atoms can neither be created nor
destroyed during a chemical reaction, although they may be rearranged, and/or their
state of matter may change.
Light spectrum
When the sun light passes through a prism it is dispersed into a continuous spectrum
of wavelengths (the rainbow).
Limiting reagent
A limiting reagent is the reagent that will be totally consumed when the chemical
reaction is complete.
Lyman series
The emission spectrum of the hydrogen atom is divided into spectral series according
to the energy level to which the electrons move down. The Lyman series is due to

GLOSSARY
electronic transitions from higher energy levels to n = 1; the wavelengths of the

emissions are in the ultra-violet region (short wavelength; high energy).
Madelung (energy ordering rule)

The order in which the orbitals are filled is given by the n+l rule. Orbitals with a lower
n+l value are filled before those with higher n+l values (n and l are the principal and
the azimutal quantum numbers respectively). When two orbitals have identical n+l
values; the orbital with a lower n value is filled first.
Metalloids
Metalloids or semi-metals show intermediate conduction properties (they are semi-
conductors). Their electronegativity values are close to 2. The valence electrons of
metalloids are localised around the nucleus but can also be moved (and therefore
conduct electricity) when excited by small inputs of energy. Semi-conductors
elements such as Si, As, Sb play an important part in microelectronic devices.
Metals
Metals are electrical conductors; they have a low electronegativity value (χ under 2).
The valence electrons of metals are more loosely attracted to the nucleus and are
free to conduct electricity. Metals make crystal lattice structures in which electrons
can flow freely.
Non-metals
Non-metals are not electrical conductors, they are characterised by a high
electronegativity value (χ over 2). The valence electrons of non-metals are strongly
attracted to their positively charged nucleus and are not available to conduct
electricity.
Oxidation state
The oxidation state (or oxidation number) is an indicator of the oxidation degree of an
atom.
Oxo-acid
Oxo-acids are polyatomic ions with polar hydrogen-oxygen bonds that can be broken
to form ions. Oxo-acids can lose one or more protons (from H-O bond breaking).
Percentage yield
Percentage yield is used to measure the effectiveness of a process. When the
process is optimal, the reaction is quantitative; the yield is 100%.
Precipitation
Precipitation is the formation of a solid in solution. The solid formed is called the
precipitate, it could fall to the bottom of the solution or remain in suspension.
Polarity (bond)

GLOSSARY
When one of the two atoms involved in a covalent bond attracts the bonding electron
pair more than the other atom, partial charges appear and the bond is polar. A
negative partial charge (δ-) appears over the atom attracting the electronic density
and a positive partial charge (δ+) appears over the other one.
Racemate
A racemate (or a racemic mixture) is a 1:1 mixture of enantiomers.
Reaction yield
The reaction yield is the amount of product obtained in a chemical reaction,
expressed in gram. The theoretical yield is the amount of product expected to be
formed and is calculated using the chemical equation. The actual yield is the amount
of product physically measured by the experimentalist.
Redox reactions
Redox reactions are reactions involving electron transfer between species. During a
redox reaction, oxidants are reduced (they gain electron(s): their oxidation states
decrease) and reducers are oxidised (they lose electrons: their oxidation states
increase).
Shape (molecule)
The shape of a molecule is the disposition of all the molecule’s atoms. It is
determined by the arrangement of the bond pairs (bp) around central atoms.
Solute
Solute can be any substance dissolved in a solvent.
Solution
A solution is made of solute dissolved in a solvent. The solution is defined as a
homogeneous mixture of one phase only.
Solvation
When ionic solids are dissolved in water, a phenomenon of solvation occurs: water
molecules form shell-layers around both anions and cations. Solvation stabilises the
charges of the ions and also separates the ions from each other.
Solvent
Solvents can be liquid, solid or a gas.
Spectator ion
A spectator ion is not modified by the chemical reaction and is found unchanged
when the reaction is complete. Spectator ions are identical on both side of the
chemical equation (as reagents and as products).
Valence electrons
Valence electrons reside in the outer atomic orbital, the “valence orbital” and are
available for bonding and chemical reactions. They are responsible for the shapes of

GLOSSARY
molecules. The number of valence electrons possessed by an element determines its

group in the Periodic Table – elements of the same group have the same number of
valence electrons.
Valence shell
The Valence Shell is the outer-shell of an atom, where valence electrons are found.
The valence electrons are responsible for the chemical properties of the elements.
Valency
The valency or valence number of an atom is the number of chemical bonds that an
atom may form to satisfy the octet rule. It is equal to the number of unpaired electron
(upe). The lone pair electrons are not counted as bonding, therefore the valency is
the number of valence electrons, less the lone pair electrons (lp).

GLOSSARY

Group 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Period
hydrogen helium
1 2
1 H He
1.0079 4.00260
lithium beryllium boron carbon nitrogen oxygen fluorine neon
3 4 5 6 7 8 9 10
2 Li Be B C N O F Ne
6.94 9.01218 10.81 12.011 14.007 15.999 18.998403 20.180
sodium magnesium aluminium silicon phosphorus sulfur chlorine argon
11 12 13 14 15 16 17 18
3 Na Mg Al Si P S Cl Ar
22.9897693 24.305 26.981539 28.086 30.97376 32.06 35.45 39.948
potassium calcium scandium titanium vanadium chromium manganese iron cobalt nickel copper zinc gallium germanium arsenic selenium bromine krypton
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.0983 40.08 44.95591 47.867 50.9415 51.996 54.93804 55.84 58.93320 58.693 63.55 65.41 69.723 72.63 74.9216 79.0 79.904 83.80
rubidium strontium yttrium zirconium niobium molybdenum technetium ruthenium rhodium palladium silver cadmium indium tin antimony tellurium iodine xenon
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.468 87.62 88.9058 91.22 92.9064 95.9 [98] 101.1 102.9055 106.42 107.868 112.41 114.82 118.71 121.760 127.6 126.9045 131.29
caesium barium hafnium tantalum tungsten rhenium osmium iridium platinum gold mercury thallium lead bismuth polonium astatine radon
55 56 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
57–71
6 Cs Ba * Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.905452 137.33 178.5 180.9479 183.84 186.207 190.2 192.22 195.08 196.96657 200.6 204.383 207.2 208.98040 [210] [210] [222]
francium radium rutherfordium dubnium seaborgium bohrium hassium meitnerium darmstadtium roentgenium copernicium ununtrium flerovium ununpentium livermorium ununseptium ununoctium
87 88 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
89–103
7 Fr Ra ** Rf Db Sg Bh Hs Mt Ds Rg Cn Uut Fl Uup Lv Uus Uuo
[223] [226] [267] [268] [269] [270] [269] [278] [281] [281] [285] [286] [289] [288] [293] [294] [294]
lanthanum cerium praseodymium neodymium promethium samarium europium gadolinium terbium dysprosium holmium erbium thulium ytterbium lutetium
57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
* Lanthanoids La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
138.9055 140.116 140.9076 144.24 [145] 150.4 151.964 157.2 158.9254 162.500 164.9303 167.26 168.9342 173.0 174.967
actinium thorium protactinium uranium neptunium plutonium americium curium berkelium californium einsteinium fermium mendelevium nobelium lawrencium
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103
** Actinoids Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
[227] 232.0381 231.0359 238.0289 [237] [244] [243] [247] [247] [251] [252] [257] [258] [259] [262]

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B17CA

Copyright © 2016 Heriot-Watt University

Distributed by Heriot-W att University

©HERIOT-WATT UNIVERSITY B17CA May 2016 v3

©HERIOT-WATT UNIVERSITY B17CA June 2015 v2

2 ATOMIC STRUCTURES AND ORBITALS .................................................................... 28

©HERIOT-WATT UNIVERSITY B17CA June 2015 v2

3 MOLECULAR SHAPE AND CHEMICAL BONDING ...................................................... 51

4 CHEMISTRY OF THE ELEMENTS OF THE MAIN GROUP ........................................... 83

©HERIOT-WATT UNIVERSITY B17CA June 2015 v2

5 ORGANIC CHEMISTRY INTRODUCTION .................................................................. 115

©HERIOT-WATT UNIVERSITY B17CA June 2015 v2

GLOSSARY ..................................................................................................................... 169

©HERIOT-WATT UNIVERSITY B17CA June 2015 v2

©HERIOT-WATT UNIVERSITY B17CA May 2016 v3

1.1.1. Chemistry: a major contributor to the global economy.

1.1.2. Atomic Structure

Ernest Rutherford (1871-

©HERIOT-WATT UNIVERSITY B17CA May 2016 v3

The Bohr model of the atom represents the atomic nucleus at

Niels Henrik David Bohr

©HERIOT-WATT UNIVERSITY B17CA May 2016 v3

Any atom can be written: X is the Chemical Symbol of the Element.

An element X is characterised by a number of protons Z (atomic number). Any element can

Example. The natural isotopes of hydrogen.

protium deuterium tritium

1.1.3. The Periodic Table of the Elements

©HERIOT-WATT UNIVERSITY B17CA May 2016 v3

Other groupings have been made and are in common usage.

• The Main Group Elements are the s- and p-block elements.

©HERIOT-WATT UNIVERSITY B17CA May 2016 v3

Valence electrons and the periodic table of the elements.

Valence electrons of the main group elements (s-block and p-block)

p-block elements (Group 13 to 18) (group number -10)

©HERIOT-WATT UNIVERSITY B17CA May 2016 v3

Valence electrons of the transition metals (d-block; group 3 to 12).

Scandium Sc: [Ar] 3d1 4s2

Chemical reactions use only the valence electrons.

1.1.4. Ions: cations and anions.

Note about hydrogen

©HERIOT-WATT UNIVERSITY B17CA May 2016 v3

1.1.5. Chemical Bonding

1.1.6. Lewis Structure

Table 1. Lewis Structures of the first 18 elements.

©HERIOT-WATT UNIVERSITY B17CA May 2016 v3

Lewis Structure of Molecules

20 ve = 8e(C) + 6e(H) +6e(O)

• Keep track of the number of valence electrons.

Lewis Structures showing the formation of Chloride ion from Chlorine.

chlorine atom electron chloride ion

• For an anion, add electrons to the valence electrons of the element.

Lewis Structures of polyatomic ions

©HERIOT-WATT UNIVERSITY B17CA May 2016 v3

Antoine de Lavoisier (1743-1794) carefully monitored the mass

Oxidation reaction of mercury in a closed system lead

1.2.1. Law of Mass Conservation

Example of the combustion of ethanol C 2 H 5 OH.

C2H5OH + O2 CO2 + H2O

• The number of carbons has to be balanced first:

C2H5OH + O2 2 CO2 + H2O