Syllabus Overview

Aims
The aims are to enable students to:
• Acquire knowledge and understanding and develop practical skills, including efficient,
accurate and safe scientific practices.
• Learn to apply the scientific method, while developing an awareness of the limitations of
scientific theories and models.
• Develop skills in data analysis, evaluation and drawing conclusions, cultivating attitudes
relevant to science such as objectivity, integrity, enquiry, initiative and inventiveness.
• Develop effective scientific communication skills, using appropriate terminology and
scientific conventions.
• Understand their responsibility to others/society and to care for the environment.
• Enjoy science and develop an informed interest in the subject that may lead to further
study.
Content Overview

AS Level subject content:

Physical chemistry
1. Atomic structure
2. Atoms, molecules and stoichiometry
3. Chemical bonding
4. States of matter
5. Chemical energetics
6. Electrochemistry
7. Equilibria
8. Reaction kinetics

Inorganic chemistry
9. The Periodic Table: chemical periodicity
10.Group 2
11.Group 17
12.Nitrogen and sulfur

Organic chemistry
13.An introduction to AS Level organic chemistry
14.Hydrocarbons
15.Halogen compounds
16.Hydroxy compounds
17.Carbonyl compounds
18.Carboxylic acids and derivatives
19.Nitrogen compounds
20.Polymerisation
21.Organic synthesis

Analysis
22.Analytical techniques

AS Level candidates also study practical skills.

Assessment Overview
Assessment Objective
CHAPTER 1
ATOMIC STRUCTURE
Learning Objectives:
1.1 Particles in the atom and atomic radius
1.2 Isotopes
1.3 Electrons, energy levels and atomic orbitals
1.4 Ionisation energy

Learning Outcomes:
→ Understand that atoms are mostly empty space surrounding a very small, dense nucleus that
contains protons and neutrons; electrons are found in shells in the empty space around the
nucleus
→ Identify and describe protons, neutrons and electrons in terms of their relative charges and relative
masses
→ Understand the terms atomic and proton number; mass and nucleon number
→ Describe the distribution of mass and charge within an atom and the behaviour of beams of
protons, neutrons and electrons moving at the same velocity in an electric field
→ Determine the numbers of protons, neutrons and electrons present in both atoms and ions given
atomic or proton number, mass or nucleon number and charge
→ State and explain qualitatively the variations in atomic radius and ionic radius across a period and
down a group
→ Define the term isotope in terms of numbers of protons and neutrons
→ Understand the notation for isotopes, where x is the mass or nucleon number and y is the atomic
or proton number
→ State that and explain why isotopes of the same element have the same chemical properties
→ State that and explain why isotopes of the same element have different physical properties, limited
to mass and density
→ Understand the terms:
•• shells, sub-shells and orbitals
•• principal quantum number (n)
•• ground state, limited to electronic configuration
→ Describe the number of orbitals making up s, p and d sub-shells, and the number of electrons
that can fill s, p and d sub-shells
→ Describe the order of increasing energy of the sub-shells within the first three shells and the 4s
and 4p sub-shells
→ Describe the electronic configurations to include the number of electrons in each shell, sub-shell
and orbital
Continued:
→ Describe the electronic configurations to include the number of electrons in each shell, sub-shell
and orbital
→ Explain the electronic configurations in terms of energy of the electrons and inter-electron
repulsion
→ Determine the electronic configuration of atoms and ions given the atomic or proton number and
charge
→ Understand and use the electrons in boxes notation
→ Describe and sketch the shapes of s and p orbitals
→ Describe a free radical as a species with one or more unpaired electrons
→ Define and use the term first ionisation energy, IE
→ Construct equations to represent first, second and subsequent ionisation energies
→ Identify and explain the trends in ionisation energies across a period and down a group of the
Periodic Table
→ Identify and explain the variation in successive ionisation energies of an element
→ Understand that ionisation energies are due to the attraction between the nucleus and the outer
electron
→ Explain the factors influencing the ionisation energies of elements in terms of nuclear charge,
atomic/ionic radius, shielding by inner shells and sub-shells and spin-pair repulsion
→ Deduce the electronic configurations of elements using successive ionisation energy data
→ Deduce the position of an element in the Periodic Table using successive ionisation energy data
INTRODUCTION:
In order to explain how chemical substances behaved, scientists first had to understand what the
substances themselves were made from. Over time, a model was developed in which all
substances were composed of atoms of elements. Originally it was thought that atoms could not
themselves be broken up into yet smaller parts, but now we understand the structure inside the
atoms themselves, and the role of electrons, protons and neutrons. We can now design and make
materials and objects almost at the atomic level.
Nanotechnology is the design and making of objects that may have a thickness of only a few
thousand atoms or less. Groups of atoms can be moved around on special surfaces. In this way
scientists hope to develop tiny machines that may help deliver medical drugs to exactly where
they are needed in the body.

Each of the blue peaks in this image is an individual molecule. The molecules can be moved
over a copper surface, making this a molecular abacus or counting device.

1.1Particles in the atom and atomic radius

Structure of an Atom
• All matter is composed of atoms, which are the smallest parts of an element that can take
place in chemical reactions
• Atoms are mostly made up of empty space around a very small, dense nucleus that contains
protons and neutrons
• The nucleus has an overall positive charge
• The protons have a positive charge and the neutrons have a neutral charge
• Negatively charged electrons are found in orbitals in the empty space around the nucleus
 The basic structure of an atom (not to scale)

Subatomic Particles
• The protons, neutrons and electrons that an atom is made up of are called subatomic
particles
• These subatomic particles are so small that it is not possible to measure their masses and
charges using conventional units (such as grams or coulombs)
• Instead, their masses and charges are compared to each other, and so are called ‘relative
atomic masses’ and ‘relative atomic charges’
• These are not actual charges and masses but charges and masses of particles relative to each
other
• Protons and neutrons have a very similar mass, so each is assigned a relative mass of 1
• Electrons are 1836 times smaller than a proton and neutron, and so their mass is often
described as being negligible
• The relative mass and charge of the subatomic particles are:
Relative mass & charge of subatomic particles table

You can see from the table how the relative mass of an electron is almost negligible
The charge of a single electron is -1.602 x 10-19 coulombs, whereas the charge of a proton
is +1.602 x 10-19 x coulombs. So, relative to each other, their charges are -1 and +1
respectively
Atoms: Key Terms
• The atomic number (or proton number) is the number of protons in the nucleus of an atom
and has the symbol Z
• The atomic number is also equal to the number of electrons present in a neutral atom of
an element
• E.g. the atomic number of lithium is 3, meaning that a neutral lithium atom has 3
protons and therefore, also has 3 electrons
• The mass number (or nucleon number) is the total number of protons + neutrons in the
nucleus of an atom, and has the symbol A
• The number of neutrons can be calculated by:
Number of neutrons = mass number – atomic number
• Protons and neutrons are also called nucleons, because they are found in the nucleus

Defining Proton Number

• The atomic number (or proton number) is the number of protons in the nucleus of an
atom. The symbol for this number is Z
• It is also the number of electrons present in an atom and determines the position of the
element on the Periodic Table
Defining Nucleon Number
• Nucleon number (or mass number) is the total number of protons and neutrons in the
nucleus of an atom. The symbol for this number is A
• The nucleon number minus the proton number gives you the number of neutrons of an
atom
• Note that protons and neutrons can collectively be called nucleons.
• The atomic number and mass number for every element is on the Periodic Table
• The mass (nucleon) and atomic (proton) number are given for each element in the
Periodic Table
Diagram showing the notation used on the Periodic Table
Determining Subatomic Structure

Determining the Subatomic Structure of Atoms & Ions

• An atom is neutral and has no overall charge

• Ions on the other hand are formed when atoms either gain or lose electrons, causing them
to become charged
• The number of subatomic particles in atoms and ions can be determined given their
atomic (proton) number, mass (nucleon) number and charge

Protons

• The atomic number of an atom and ion determines which element it is

• Therefore, all atoms and ions of the same element have the same number of protons
(atomic number) in the nucleus
o E.g. lithium has an atomic number of 3 (three protons) whereas beryllium has
atomic number of 4 (4 protons)
• The number of protons equals the atomic (proton) number
• The number of protons of an unknown element can be calculated by using its mass
number and number of neutrons:

Mass number = number of protons + number of neutrons

Number of protons = mass number – number of neutrons

Determine the number of protons

Question:
Determine the number of protons of the following ions and atoms:
1. Mg²⁺ ion
2. Carbon atom
3. An unknown atom of element X with mass number 63 and 34 neutrons
Answer
• Answer 1: The atomic number of a magnesium atom is 12 suggesting that the
number of protons in the magnesium element is 12
• Therefore the number of protons in a Mg²⁺ion is also 12
• Answer 2: The atomic number of a carbon atom is 6 suggesting that a carbon atom
has 6 protons in its nucleus
• Answer 3: Use the formula to calculate the number of protons
Number of protons = mass number – number of neutrons
Number of protons = 63 – 34
Number of protons = 29
• Element X is therefore copper
Electrons (symbol e⁻)

• These subatomic particles move very fast around the nucleus

• An atom is neutral and therefore has the same number of protons and electrons
• They move in orbital paths called shells
• Ions have a different number of electrons to their atomic number depending on their
charge
o A positively charged ion has lost electrons and therefore has fewer electrons than
protons
o A negatively charged ion has gained electrons and therefore has more electrons
than protons

Determine the number of electrons

Question:
Determine the number of protons of the following ions and atoms:
1. Mg²⁺ ion
2. Carbon atom
3. An unknown atom of element X with mass number 63 and 34 neutrons
Answer
• Answer 1: The atomic number of a magnesium atom is 12 suggesting that the number
of protons in the neutral magnesium atom is 12
o However, the 2+ charge in Mg2+ ion suggests it has lost two electrons
o It only has 10 electrons left now
• Answer 2: The atomic number of a carbon atom is 6 suggesting that the neutral
carbon atom has 6 electrons orbiting around the nucleus
• Answer 3: The number of protons of element X can be calculated by:
Number of protons = mass number – number of neutrons
Number of protons = 63 – 34
Number of protons = 29
o The neutral atom of element X therefore also has 29 electrons

Neutrons

• The mass and atomic numbers can be used to find the number of neutrons in ions and
atoms:

Number of neutrons = mass number (A) – number of protons (Z)

 Determine the number of neutrons
Question:
Determine the number of protons of the following ions and atoms:
1. Mg²⁺ ion
2. Carbon atom
3. An unknown atom of element X with mass number 63 and 34 neutrons
Answer
• Answer 1: The atomic number of a magnesium atom is 12 and its mass number is 24
Number of neutrons = mass number (A) – number of protons (Z)
Number of neutrons = 24 – 12
Number of neutrons = 12
o The Mg2+ ion has 12 neutrons in its nucleus
• Answer 2: The atomic number of a carbon atom is 6 and its mass number is 12
Number of neutrons = mass number (A) – number of protons (Z)
Number of neutrons = 12 – 6
Number of neutrons = 6
o The carbon atom has 6 neutrons in its nucleus
• Answer 3: The atomic number of an element X atom is 29 and its mass number is 63

Mass, Charge & Subatomic Particles

Mass & Charge Distribution
• The mass of an atom is concentrated in the nucleus, because the nucleus contains the
heaviest subatomic particles (the neutrons and protons)
o The mass of the electron is negligible
• The nucleus is also positively charged due to the protons
• Electrons orbit the nucleus of the atom, contributing very little to its overall mass, but
creating a ‘cloud’ of negative charge
• The electrostatic attraction between the positive nucleus and negatively charged
electrons orbiting around it is what holds an atom together

The mass of the atom is concentrated in the positively charged nucleus which is
attracted to the negatively charged electrons orbiting around it
Behaviour of Subatomic Particles in an Electric Field

• Protons, neutrons and electrons behave differently when they move at the same velocity
in an electric field
• When a beam of electrons is fired past the electrically charged plates, the electrons are
deflected very easily away from the negative plate towards the positive plate
o This proves that the electrons are negatively charged; like charges repel each
other
o It also shows that electrons have a very small mass, as they are easily deflected
• A beam of protons is deflected away from the positive plate and towards the negative
plate
o This proves that the proton is positively charged
o As protons are deflected less than electrons, this also shows that protons are
heavier than electrons
• A beam of neutrons is not deflected at all
o Which proves that the particle is neutral in character; it is not attracted to, or
repelled by, the negative or positive plate

The lighter electrons undergo much more deflection than the protons
Atomic & Ionic Radius

Atomic radius

• The atomic radius of an element is a measure of the size of an atom

• It is half the distance between the two nuclei of two covalently bonded atoms of the same
type

The atomic radius of a hydrogen atom is determined by halving the distance between the
nuclei of two hydrogen atoms covalently bonded

• Atomic radii show predictable patterns across the Periodic Table

o They generally decrease across each Period
o They generally increase down each Group
• These trends can be explained by the electron shell theory
o Atomic radii decrease as you move across a Period as the atomic number
increases (increased positive nuclear charge) but at the same time extra electrons
are added to the same principal quantum shell
o The larger the nuclear charge, the greater the pull of the nuclei on the electrons
which results in smaller atoms
o Atomic radius increase moving down a Group as there is an increased number of
shells going down the Group
o The electrons in the inner shells repel the electrons in the outermost shells,
shielding them from the positive nuclear charge
o This weakens the pull of the nuclei on the electrons resulting in larger atoms
 Trends in the atomic radii across a period and down a group

• The diagram shows that the atomic radius increases sharply between the noble gas at the
end of each period and the alkali metal at the beginning of the next period
• This is because the alkali metals at the beginning of the next period have one extra
principal quantum shell
o This increases shielding of the outermost electrons and therefore increases the
atomic radius

Ionic radius
• The ionic radius of an element is a measure of the size of an ion
• Ionic radii show predictable patterns
o Ionic radii increase with increasing negative charge
o Ionic radii decrease with increasing positive charge
• These trends can also be explained by the electron shell theory
o Ions with negative charges are formed by atoms accepting extra electrons while
the nuclear charge remains the same
o The outermost electrons are further away from the positively charged nucleus
and are therefore held only weakly to the nucleus which increases the ionic radius
o The greater the negative charge, the larger the ionic radius
o Positively charged ions are formed by atoms losing electrons
o The nuclear charge remains the same but there are now fewer electrons which
undergo a greater electrostatic force of attraction to the nucleus which
decreases the ionic radius
o The greater the positive charger, the smaller the ionic radius
 Trends in the ionic radii across a period and down a group

1.2 ISOTOPES

All atoms of the same element have the same number of protons. However, they may have
different numbers of neutrons. Atoms of the same element that have differing numbers of neutrons
are called isotopes. Isotopes are atoms of the same element that contain the same number of
protons and electrons but a different number of neutrons.
Isotopes of a particular element have the same chemical properties because they have the
same number of electrons. They have slightly different physical properties, such as small
differences in density.
We can write symbols for isotopes. The symbol for an isotope is the chemical symbol (or
word) followed by a dash and then the mass number. We write the nucleon number at the top
left of the chemical symbol and the proton number at the bottom left. The symbol for the isotope
of boron with 5 protons and 11 nucleons is written:
When writing generally about isotopes, chemists also name them by omitting the proton number
and placing the nucleon number after the name. For example, the isotopes of hydrogen can be
called hydrogen-1, hydrogen-2 and hydrogen-3.

The atomic structure and symbols of the three isotopes of hydrogen

Isotopes: Chemical & Physical Properties

• Isotopes have similar chemical properties but different physical properties

Chemical properties
• Isotopes of the same element display the same chemical characteristics
• This is because they have the same number of electrons in their outer shells
• Electrons take part in chemical reactions and therefore determine the chemistry of an
atom

Physical properties
• The only difference between isotopes is the number of neutrons
• Since these are neutral subatomic particles, they only add mass to the atom
• As a result of this, isotopes have different physical properties such as small differences
in their mass and density

1.3 Electrons, Energy Levels and Atomic Orbitals

Electronic Structure
Electron Shells: Basics
Shells

• The arrangement of electrons in an atom is called the electronic configuration

• Electrons are arranged around the nucleus in principal energy levels or principal
quantum shells
• Principal quantum numbers (n) are used to number the energy levels or quantum shells
o The lower the principal quantum number, the closer the shell is to the nucleus
o The higher the principal quantum number, the lesser the energy of the shell
• Each principal quantum number has a fixed number of electrons it can hold
o n = 1 : up to 2 electrons
o n = 2 : up to 8 electrons
o n = 3 : up to 18 electrons
 o n = 4 : up to 32 electrons

Electrons are arranged in principal quantum shells, which are numbered by principal
quantum numbers

Subshells

• The principal quantum shells are split into subshells which are given the letters s, p and d
o Elements with more than 57 electrons also have an f shell
o The energy of the electrons in the subshells increases in the order s < p < d
• The order of subshells appear to overlap for the higher principal quantum shells as seen
in the diagram below:
 Electrons are arranged in principal quantum shells, which are numbered by principal
quantum numbers

Orbitals

• Subshells contain one or more atomic orbitals

• Orbitals exist at specific energy levels and electrons can only be found at these specific
levels, not in between them
o Each atomic orbital can be occupied by a maximum of two electrons
• This means that the number of orbitals in each subshell is as follows:
o s : one orbital (1 x 2 = total of 2 electrons)
o p : three orbitals ( 3 x 2 = total of 6 electrons)
o d : five orbitals (5 x 2 = total of 10 electrons)
o f : seven orbitals (7 x 2 = total of 14 electrons)
• The orbitals have specific 3-D shapes

Representation of orbitals (the dot represents the nucleus of the atom) showing spherical s
orbitals (a), p orbitals containing ‘lobes’ along the x, y and z axis

Note that the shape of the d orbitals is not required at AS Level

 An overview of the shells, subshells and orbitals in an atom

Ground state

• The ground state is the most stable electronic configuration of an atom which has the
lowest amount of energy
• This is achieved by filling the subshells of energy with the lowest energy first (1s)
• The order of the subshells in terms of increasing energy does not follow a regular pattern
at n= 3 and higher

The ground state of an atom is achieved by filling the lowest energy subshells first

Electron Subshells & Orbitals

Electron Orbitals

• Each shell can be divided further into subshells, labelled s, p, d and f

• Each subshell can hold a specific number of orbitals:
o s subshell : 1 orbital
o p subshell : 3 orbitals labelled px, py and pz
o d subshell : 5 orbitals
 o f subshell : 7 orbitals
• Each orbital can hold a maximum number of 2 electrons so the maximum number of
electrons in each subshell are as follows:
o s : 1 x 2 = total of 2 electrons
o p : 3 x 2 = total of 6 electrons
o d : 5 x 2 = total of 10 electrons
o f : 7 x 2 = total of 14 electrons
• In the ground state, orbitals in the same subshell have the same energy and are said to be
degenerate, so the energy of a px orbital is the same as a py orbital

Shells are divided into subshells which are further divided into orbitals
 Summary of the arrangement of electrons in atoms table

Subshells & Energy

• The principal quantum shells increase in energy with increasing principal quantum
number
o E.g. n = 4 is higher in energy than n = 2
• The subshells increase in energy as follows: s ＜ p ＜ d ＜ f
o The only exception to these rules is the 3d orbital which has slightly higher
energy than the 4s orbital
o Because of this, the 4s orbital is filled before the 3d orbital
• All the orbitals in the same subshell have the same energy and are said to be degenerate
o E.g. px, py and pz are all equal in energy
 Relative energies of the shells and subshells

The s & p Orbitals

s orbitals

• The s orbitals are spherical in shape

• The size of the s orbitals increases with increasing shell number
o E.g. the s orbital of the third quantum shell (n = 3) is bigger than the s orbital of
the first quantum shell (n = 1)

The s orbitals become larger with increasing principal quantum number

p orbitals
• The p orbitals are dumbbell-shaped
• Every shell has three p orbitals except for the first one (n = 1)
• The p orbitals occupy the x, y and z-axis and point at right angles to each other so are
oriented perpendicular to one another
• The lobes of the p orbitals become larger and longer with increasing shell number
 The p orbitals become larger and longer with increasing principal quantum number

Electron Configuration
Electron Configurations: Basics

• The electron configuration gives information about the number of electrons in each
shell, subshell and orbital of an atom
• The subshells are filled in order of increasing energy

The electron configuration shows the number of electrons occupying a subshell in a specific
shell

Electron Configurations: Explained

• Electrons can be imagined as small spinning charges which rotate around their own axis
in either a clockwise or anticlockwise direction
o The spin of the electron is represented by its direction

Electrons can spin either in a clockwise or anticlockwise direction around their own axis
 • Electrons with similar spin repel each other which is also called spin-pair repulsion
• Electrons will therefore occupy separate orbitals in the same subshell to minimize this
repulsion and have their spin in the same direction
o Eg. if there are three electrons in a p subshell, one electron will go into each px,
py and pz orbital

Electron configuration: three electrons in a p subshell

• Electrons are only paired when there are no more empty orbitals available within a
subshell in which case the spins are the opposite spins to minimize repulsion
o Eg. if there are four electrons in a p subshell, one p orbital contains 2 electrons
with opposite spin and two orbitals contain one electron only

Electron configuration: four electrons in a p subshell

• The principal quantum number indicates the energy level of a particular shell but also
indicates the energy of the electrons in that shell
o A 2p electron is in the second shell and therefore has an energy corresponding to
n=2
• Even though there is repulsion between negatively charged electrons (inter-electrons
repulsion), they occupy the same region of space in orbitals
• This is because the energy required to jump to successive empty orbital is greater than
the inter-electron repulsion
• For this reason, they pair up and occupy the lower energy levels first

Electron Box Notation

• The electron configuration can also be represented using the electrons in boxes
notation
• Each box represents an atomic orbital
• The boxes are arranged in order of increasing energy from lowest to highest
• The electrons are represented by opposite arrows to show the spin of the electrons
o Eg. the box notation for titanium is shown below
o Note that since the 3d subshell cannot be either full or half full, the second 4s
electron is not promoted to the 3d level and stays in the 4s orbital

The electrons in Titanium are arranged in their orbitals as shown. Electrons occupy the lowest
energy levels first before filling those with higher energy
Free Radicals
• A free radical is a species with one or more unpaired electron
• The unpaired electron in the free radical is shown as a dot
o Eg. a chlorine free radical has the electron configuration 1s22s22p63s23p5
o Two of the three p orbitals have paired electrons whereas one of them has an
unpaired electron

One of the p orbitals has unpaired electrons in a chlorine radical

Determining Electronic Configurations
• Writing out the electronic configuration tells us how the electrons in an atom or ion are
arranged in their shells, subshells and orbitals
• This can be done using the full electron configuration or the shorthand version
o The full electron configuration describes the arrangement of all electrons from the
1s subshell up
o The shorthand electron configuration includes using the symbol of the nearest
preceding noble gas to account for however many electrons are in that noble gas
• Ions are formed when atoms lose or gain electrons
o Negative ions are formed by adding electrons to the outer subshell
o Positive ions are formed by removing electrons from the outer subshell
o The transition metals fill the 4s subshell before the 3d subshell but lose electrons
from the 4s first and not from the 3d subshell (the 4s subshell is lower in energy)
• The Periodic Table is split up into four main blocks depending on their electronic
configuration:
o s block elements
▪ Have their valence electron(s) in an s orbital
o p block elements
▪ Have their valence electron(s) in a p orbital
o d block elements
▪ Have their valence electron(s) in a d orbital
o f block elements
▪ Have their valence electron(s) in an f orbital
 The elements can be divided into four blocks according to their outer shell electron
configuration
Exceptions
• Chromium and copper have the following electron configurations, which are different to
what you may expect:
o Cr is [Ar] 3d5 4s1 not [Ar] 3d4 4s2
o Cu is [Ar] 3d10 4s1 not [Ar] 3d9 4s2
• This is because the [Ar] 3d5 4s1 and [Ar] 3d10 4s1 configurations are energetically stable

1.4 Ionisation Energy

First Ionisation Energy
• The Ionisation Energy (IE) of an element is the amount of energy required to remove
one mole of electrons from one mole of gaseous atoms of an element to form one mole
of gaseous ions
• Ionisation energies are measured under standard conditions which are 298 K and 1 atm
• The units of IE are kilojoules per mole (kJ mol-1)
• The first ionisation energy (IE1) is the energy required to remove one mole of electrons
from one mole of atoms of an element to form one mole of 1+ ions
o E.g. the first ionisation energy of gaseous calcium:
Ca(g) → Ca+ (g) + e– IE1 = +590 kJ mol-1
Ionisation Energies: Equations
• The second ionisation energy (IE2) is the energy required to remove the second mole of
electrons from each +1 ion in a mole of gaseous +1 ions, to form one mole of +2 ions
• The third ionisation energy (IE3) is the energy required to remove the third mole of
electrons from each +2 ion in a mole of gaseous +2 ions, to form one mole of +3 ions
• The electrons from an atom can be continued to be removed until only the nucleus is left
• This sequence of ionisation energies is called successive ionisation energies
Successive Ionisation Energies of Beryllium Table
Ionisation Energies: Trends

• Ionisation energies show periodicity – a trend across a period of the Periodic Table
• As could be expected from their electronic configuration, the group I metals have a
relatively low ionisation energy, whereas the noble gases have very high ionisation
energies
• The size of the first ionisation energy is affected by four factors:
o Size of the nuclear charge
▪ The nuclear charge increases with increasing atomic number, which means
that there are greater attractive forces between the nucleus and electrons,
so more energy is required to overcome these attractive forces when
removing an electron
o Distance of outer electrons from the nucleus
▪ Electrons in shells that are further away from the nucleus are less attracted
to the nucleus – the nuclear attraction is weaker – so the further the outer
electron shell is from the nucleus, the lower the ionisation energy
o Shielding effect of inner electrons
▪ The shielding effect is when the electrons in full inner shells repel
electrons in outer shells, preventing them from feeling the full nuclear
charge, so the more shells an atom has, the greater the shielding effect,
and the lower the ionisation energy
o Spin-pair repulsion
▪ Electrons in the same atomic orbital in a subshell repel each other more
than electrons in different atomic orbitals which makes it easier to remove
an electron (which is why the first ionization energy is always the lowest)
• So, the first ionisation energy increases across a period and decreases down a group

A graph showing the ionisation energies of the elements hydrogen to sodium

Ionisation energy across a period

• The ionisation energy over a period increases due to the following factors:
o Across a period the nuclear charge increases
o This causes the atomic radius of the atoms to decrease, as the outer shell is
pulled closer to the nucleus, so the distance between the nucleus and the outer
electrons decreases
o The shielding by inner shell electrons remain reasonably constant as electrons are
being added to the same shell
 o It becomes harder to remove an electron as you move across a period; more
energy is needed
o So, the ionisation energy increases
• There is a rapid decrease in ionisation energy between the last element in one period,
and the first element in the next period because:
o There is increased distance between the nucleus and the outer electrons as you
have added a new shell
o There is increased shielding by inner electrons because of the added shell
o These two factors outweigh the increased nuclear charge
• There is a slight decrease in IE1 between beryllium and boron as the fifth electron in
boron is in the 2p subshell, which is further away from the nucleus than the 2s subshell of
beryllium
o Beryllium has a first ionisation energy of 900 kJ mol-1 as its electron
configuration is 1s2 2s2
o Boron has a first ionisation energy of 800 kJ mol-1 as its electron configuration is
1s2 2s2 2px1
• There is a slight decrease in IE1 between nitrogen and oxygen and phosphorus due to
spin-pair repulsion in the 2px orbital of oxygen
o Nitrogen has a first ionisation energy of 1400 kJ mol-1 as its electron
configuration is 1s2 2s2 2px1 2py1 2pz1
o Oxygen has a first ionisation energy of 1310 kJ mol-1 as its electron
configuration is 1s2 2s2 2px2 2py1 2pz1

Ionisation energy down a group

• The ionisation energy down a group decreases due to the following factors:
o The number of protons in the atom is increased, so the nuclear charge increases
o But, the atomic radius of the atoms increases as you are adding more shells of
electrons, making the atoms bigger
o So, the distance between the nucleus and outer electron increases as you descend
the group
o The shielding by inner shell electrons increases as there are more shells of
electrons
o These factors outweigh the increased nuclear charge, meaning it becomes easier
to remove the outer electron as you descend a group
o So, the ionisation energy decreases

Ionisation energy trends across a period & going down a group table
Successive ionisation energies of an element
• The successive ionisation energies of an element increase
• This is because once you have removed the outer electron from an atom, you have
formed a positive ion
• Removing an electron from a positive ion is more difficult than from a neutral atom
• As more electrons are removed, the attractive forces increase due to decreasing
shielding and an increase in the proton to electron ratio
• The increase in ionisation energy, however, is not constant and is dependent on the
atom’s electronic configuration
• Taking calcium as an example:
Ionisation energies of calcium table

• The first electron removed has a low IE1 as it is easily removed from the atom due to the
spin-pair repulsion of the electrons in the 4s orbital
• The second electron is more difficult to remove than the first electron as there is no spin-
pair repulsion
• The third electron is much more difficult to remove than the second one corresponding
to the fact that the third electron is in a principal quantum shell which is closer to the
nucleus (3p)
• Removal of the fourth electron is more difficult as the orbital is no longer full, and there
is less spin-pair repulsion
Ionisation Energies: Explained
• Energy is required to remove an outer shell electron as this involves breaking the
attractive forces between the electron and the positively charged nucleus
• There are several factors which affect the magnitude of the ionisation energy:
• Nuclear charge
o Positive nuclear charge increases with increasing number of protons
o The greater the positive charge, the greater the attractive forces between the outer
electron(s) and the nucleus
o More energy is required to overcome these forces so ionisation energy increases
with increasing nuclear charge
• Shielding
o Electrons repel each other and electrons occupying the inner shells repel electrons
located in shells further outside the nucleus and prevent them from feeling the full
effect of the nuclear charge
o The greater the shielding effect is, the weaker the attractive forces between the
positive nucleus and the negatively charged electrons
o Less energy is required to overcome the weakened attractive forces so ionisation
energy decreases with increasing shielding effects

Shielding makes it easier to remove the outermost electrons

• Atomic/ionic radius
o The larger the radius, the greater the distance between the nucleus and the outer
shell electron(s)
o Increasing distance weakens the strength of the attractive forces
o Larger atoms/ions also result in greater shielding due to the presence of more
inner electrons
o Less energy is required to remove the outer shell electron(s) so ionisation energy
decreases with increasing atomic/ionic radius
• Spin-pair repulsion
o Spin pair repulsion occurs when the electron being removed is spin paired with
another electron in the same orbital
o The proximity of the like charges of electrons in the orbital results in repulsion
o Less energy is required to remove one of the electrons so ionisation energy
decreases when there is spin-pair repulsion
 Summary of factors affecting ionisation energies of atoms

Ionisation Energies: Electronic Configuration

• Successive ionisation data can be used to:
o Predict or confirm the simple electronic configuration of elements
o Confirm the number of electrons in the outer shell of an element
o Deduce the Group an element belongs to in the Periodic Table
• By analyzing where the large jumps appear and the number of electrons removed when
these large jumps occur, the electron configuration of an atom can be determined
• Na, Mg and Al will be used as examples to deduce the electronic configuration and
positions of elements in the Periodic Table using their successive ionisation energies

Successive ionisation energies table

Sodium
• For sodium, there is a huge jump from the first to the second ionisation energy,
indicating that it is much easier to remove the first electron than the second
• Therefore, the first electron to be removed must be the last electron in the valence shell
thus Na belongs to group I
• The large jump corresponds to moving from the 3s to the full 2p subshell
Na 1s2 2s2 2p6 3s1
Magnesium
• There is a huge increase from the second to the third ionisation energy, indicating that it
is far easier to remove the first two electrons than the third
 • Therefore the valence shell must contain only two electrons indicating that magnesium
belongs to group II
• The large jump corresponds to moving from the 3s to the full 2p subshell
Mg 1s2 2s2 2p6 3s2
Aluminium
• There is a huge increase from the third to the fourth ionisation energy, indicating that it
is far easier to remove the first three electrons than the fourth
• The 3p electron and 3s electrons are relatively easy to remove compared with the 2p
electrons which are located closer to the nucleus and experience greater nuclear charge
• This is due to weakened shielding effects through the loss of three electrons
• The large jump corresponds to moving from the third shell to the second shell
Al 1s2 2s2 2p6 3s2 3p1

Summary
• Every atom has an internal structure with a nucleus in the centre and the negatively
charged electrons arranged in ‘shells’ outside the nucleus.
• Most of the mass of the atom is in the nucleus, which contains protons (positively
charged) and neutrons (uncharged).
• Beams of protons and electrons are deflected by electric fields but neutrons are not.
• All atoms of the same element have the same number of protons. This is the proton
number (Z), which is also called the atomic number.
• The nucleon number, which is also called the mass number (A), is the total number of
protons and neutrons in an atom.
• The number of neutrons in an atom is found by subtracting the proton number from the
nucleon number (A – Z).
• In a neutral atom, number of electrons = number of protons. When there are more
protons than electrons, the atom becomes a positive ion. When there are more electrons
than protons, a negatively charged ion is formed.
• Isotopes are atoms with the same atomic number but different nucleon numbers. They
only differ in the number of neutrons they contain.
• Electrons in an atom can exist only in certain energy levels (shells) outside the nucleus.
• The main energy levels (shells) are given principal quantum numbers n = 1, 2, 3, 4, etc.
The lowest energy level (n = 1) is closest to the nucleus.
• The shells may be divided into subshells known as s, p and d subshells, which can hold
a maximum of 2, 6 and 10 electrons, respectively.
• The region of space in which an electron is likely to be found is called an orbital. Each
subshell has a number of orbitals which can each hold a maximum of two electrons.
Subshells s, p and d have 1, 3 and 5 orbitals, respectively.
• The s orbitals are spherical in shape. The p orbitals have two ‘lobes’.
• When two electrons are present in an orbital they spin in opposite directions and are
said to be paired.
• The electronic configuration of atoms is found by adding electrons to each orbital
starting from those in the lowest energy level.
• When electrons are added to orbitals in the same subshell they go into separate orbitals
if possible.
• Electrons pair up where this is not possible.
• The 1st ionisation energy of an element is the energy needed to remove one electron
from each atom in
• one mole of atoms of the element in the gaseous
• state (to form gaseous 1+ ions).
• ■ The ionisation energies needed to remove the first,
• second, third, fourth, etc., electrons from each
Continued:
• When electrons are added to orbitals in the same subshell they go into separate orbitals if
possible.
• Electrons pair up where this is not possible.
• The 1st ionisation energy of an element is the energy needed to remove one electron from
each atom in one mole of atoms of the element in the gaseousstate (to form gaseous 1+
ions).
• The ionisation energies needed to remove the first, second, third, fourth, etc., electrons
from each atom or ion in a mole of gaseous atoms are called successive ionisation
energies.
• The magnitude of the ionisation energy depends on these four factors:
– the distance of the electron from the nucleus
– the number of positive charges in the nucleus
– the degree of shielding of outer electrons by inner electron shells
– spin-pair repulsion.
• The trends in 1st ionisation energy of the elements across a period and down a group can
be explained using the four factors above.
• Values of successive ionisation energies of atoms provide evidence for their electronic
configuration.
CHAPTER 2
ATOMS, MOLECULES & STOICHIOMETRY
Learning Objectives:
2.1 Relative masses of atoms and molecules
2.2 The mole and the Avogadro constant
2.3 Formulae
2.4 Reacting masses and volumes (of solutions and gases)

Learning Outcomes:
Candidates should be able to:

→ Define the unified atomic mass unit as one twelfth of the mass of a carbon-12 atom
→ Define relative atomic mass, Ar, relative isotopic mass, relative molecular mass, Mr, and relative
formula mass in terms of the unified atomic mass unit
→ Define and use the term mole in terms of the Avogadro constant
→ Write formulae of ionic compounds from ionic charges and oxidation numbers (shown by a
Roman numeral), including:
(a) the prediction of ionic charge from the position of an element in the Periodic Table
(b) recall of the names and formulae for the following ions: NO3⁻, CO3²⁻, SO4²⁻, OH⁻, NH4⁺,
Zn²⁺, Ag⁺,HCO3⁻, PO4³⁻
→ Write and construct equations (which should be balanced), including ionic equations (which
should not include spectator ions) and use appropriate state symbols in equations
→ Define and use the terms empirical and molecular formula
→ Understand and use the terms anhydrous, hydrated and water of crystallisation
→ Calculate empirical and molecular formulae, using given data
→ Perform calculations including use of the mole concept, involving:
(a) reacting masses (from formulae and equations) including percentage yield calculations
(b) volumes of gases (e.g. in the burning of hydrocarbons)
(c) volumes and concentrations of solutions
(d) limiting reagent and excess reagent
(When performing calculations, candidates’ answers should reflect the number of significant
figures given or asked for in the question. When rounding up or down, candidates should ensure
that significant figures are neither lost unnecessarily nor used beyond what is justified (see also
Mathematical requirements section).)
(e) deduce stoichiometric relationships from calculations such as those in 2.4.1 (a)–(d)
INTRODUCTION:
The arrangement of the electrons within each atom determines how that atom interacts with other
atoms and with its surroundings. The electrons are organised into different levels of energy and
understanding the effects of this arrangement is key to understanding chemistry itself. We can also
make use of these electron levels. For example, causing an electron to move between energy levels
can cause energy to be emitted or absorbed. Sometimes, we can see this in the form of light.

Electrons moving between energy levels are the source of this light energy. Chemicals in the
tubes are said to be ‘chemiluminescent’.

2.1Relative Masses of Atoms and Molecules

Relative Masses
Atomic Mass Unit
• The mass of a single atom is so small that it is impossible to weigh it directly
• Atomic masses are therefore defined in terms of a standard atom which is called the
unified atomic mass unit
• This unified atomic mass is defined as one-twelfth of the mass of a carbon-12 isotope
• The symbol for the unified atomic mass is u (often Da, Dalton, is used as well)
• 1 u = 1.66 x 10-27 kg

Relative atomic mass, Ar

• The relative atomic mass (Ar) of an element is the ratio of the average mass of the
atoms of an element to the unified atomic mass unit
• The relative atomic mass is determined by using the average mass of the isotopes of a
particular element
• The Ar has no units as it is a ratio and the units cancel each other out
Relative isotopic mass
• The relative isotopic mass is the mass of a particular atom of an isotope compared to the
value of the unified atomic mass unit
• Atoms of the same element with a different number of neutrons are called isotopes
• Isotopes are represented by writing the mass number as 20Ne, or neon-20 or Ne-20
o To calculate the average atomic mass of an element the percentage abundance is
taken into account
o Multiply the atomic mass by the percentage abundance for each isotope and add
them all together
o Divide by 100 to get average relative atomic mass
o This is known as the weighted average of the masses of the isotopes

Relative molecular mass, Mr

• The relative molecular mass (Mr) is the ratio of weighted average mass of a molecule of
a molecular compound to the unified atomic mass unit
• The Mr has no units

• The Mr can be found by adding up the relative atomic masses of all atoms present in one
molecule
• When calculating the Mr the simplest formula for the compound is used, also known as
the formula unit
o Eg. silicon dioxide has a giant covalent structure, however the simplest formula
(the formula unit) is SiO2

Relative formula mass, Mr

• The relative formula mass (Mr) is used for compounds containing ions
• It has the same units and is calculated in the same way as the relative molecular mass
• In the table above, the Mr for potassium carbonate, calcium hydroxide and ammonium
sulfates are relative formula masses
2.2The Mole & Avogadro Constant
Mole & Avogadro Constant
• The Avogadro constant (NA or L) is the number of particles equivalent to the relative
atomic mass or molecular mass of a substance
o The Avogadro constant applies to atoms, molecules, ions and electrons
• The value of NA is 6.02 x 1023 g mol-1
• The mass of a substance with this number of particles is called a mole (mol)
o The mass of a substance containing the same number of fundamental units as
there are atoms in exactly 12.00 g of 12C
• One mole of any element is equal to the relative atomic mass of that element in grams
o One mole of carbon, that is if you had 6.02 x 1023 atoms of carbon in your hand,
would have a mass of 12 g
o One mole of water would have a mass of (2 x 1 + 16) = 18 g

Worked Example: Moles

Question:
Determine the number of atoms, molecules and the relative mass of 1 mole of:
4. Na
5. H₂
6. NaCl

Answer 1
The relative atomic mass of Na is 22.99
Therefore, 1 mol of Na has a mass of 22.99 g mol-1
1 mol of Na will contain 6.02 x 1023 atoms of Na (Avogadro’s constant)
Answer 2
The relative atomic mass of H is 1.005
Since there are 2 H atoms in H2, the mass of 1 mol of H2 is (2 x 1.005) 2.01 g
mol-1
1 mol of H2 will contain 6.02 x 1023 molecules of H2
Since there are 2 H atoms in H2, 1 mol of H2 will contain 1.204 x 1024 H atoms
Answer 3
The relative atomic mass of Na and Cl is 22.99 and 35.45 respectively
Therefore, 1 mol of NaCl has a mass of (22.99 + 35.45) 58.44 g mol-1
1 mol of NaCl will contain 6.02 x 1023 molecules of NaCl
Since there are Na and Cl atoms in NaCl, 1 mol of NaCl will contain 1.204 x 1024
atoms in total
2.3 Formulae
Formulae of Ionic Compounds
• Ionic compounds are formed from a metal and a nonmetal bonded together
• Ionic compounds are electrically neutral; the positive charges equal the negative charges
Charges on positive ions
• All metals form positive ions
o There are some non-metal positive ions such as ammonium, NH4+, and hydrogen,
H+
• The metals in Group 1, Group 2 and Group 13 have a charge of 1+ and 2+ and 3+
respectively
• The charge on the ions of the transition elements can vary which is why Roman
numerals are often used to indicate their charge
• Roman numerals are used in some compounds formed from transition elements to show
the charge (or oxidation state) of metal ions
o Eg. in copper (II) oxide, the copper ion has a charge of 2+ whereas in copper (III)
nitrate, the copper has a charge of 3+
Non-metal ions
• The non-metals in group 15 to 17 have a negative charge and have the suffix ‘ide’
o Eg. nitride, chloride, bromide, iodide
• Elements in group 17 gain 1 electron so have a 1- charge, eg. Br–
• Elements in group 16 gain 2 electrons so have a 2- charge, eg. O2-
• Elements in group 15 gain 3 electrons so have a 3- charge, eg. N3-
• There are also more complex negative ions, which are negative ions made up of more
than one type of atom

The charges of simple ions depend on their position in the Periodic Table
Formulae of ionic compounds table

Worked Example:Formulae
Question:
Determine the formulae of the following ionic compounds:
1. Magnesium chloride
2. Iron (III) Oxide
3. Aluminium nitrate
Answer
Answer 1: Magnesium chloride
• Magnesium is in Group 2 so has a charge of 2+
• Chlorine is in group 17 so has a charge of 1-
• Magnesium needs two chlorine atoms for each magnesium atom to be balanced so
the formula is MgCl2
Answer 2: Iron (III) oxide
• The Roman numeral states that iron has a charge of 3+
• Oxygen is in group 16 so has a charge of 2-
• The charges need to be equal so 2 iron to 3 oxygen atoms will balance
electrically, so the formula is Fe2O3
Answer 3: Aluminum nitrate
• Aluminium is in group 13 so has a charge of 3+
• Nitrate is a compound ion and has a charge of 1-
• The complex ion needs to be placed in a bracket if more than 1 is needed
• The formula of aluminium nitrate is Al(NO3)3
Balancing Equations
• A symbol equation is a shorthand way of describing a chemical reaction using chemical
symbols to show the number and type of each atom in the reactants and products
• A word equation is a longer way of describing a chemical reaction using only words to
show the reactants and products
Balancing equations
• During chemical reactions, atoms cannot be created or destroyed
• The number of each atom on each side of the reaction must therefore be the same
o E.g. the reaction needs to be balanced
• When balancing equations remember:
o Not to change any of the formulae
o To put the numbers used to balance the equation in front of the formulae
o To balance firstly the carbon, then the hydrogen and finally the oxygen in
combustion reactions of organic compounds
• When balancing equations follow the following the steps:
o Write the formulae of the reactants and products
o Count the numbers of atoms in each reactant and product
o Balance the atoms one at a time until all the atoms are balanced
o Use appropriate state symbols in the equation
• The physical state of reactants and products in a chemical reaction is specified by using
state symbols
o (s) solid
o (l) liquid
o (g) gas
o (aq) aqueous
Ionic equations
• In aqueous solutions ionic compounds dissociate into their ions
• Many chemical reactions in aqueous solutions involve ionic compounds, however only
some of the ions in solution take part in the reactions
• The ions that do not take part in the reaction are called spectator ions
• An ionic equation shows only the ions or other particles taking part in a reaction,
without showing the spectator ions
 Balance the ionic equations:
Magnesium + Oxygen → Magnesium oxide

Answer:
Step 1: Write out the symbol equation showing reactants and products
Mg + O2 → MgO
Step 2: Count the numbers of atoms in each reactant and product

Step 3: Balance the atoms one at a time until all the atoms are balanced
2Mg + O2 → 2MgO
This is now showing that 2 moles of magnesium react with 1 mole of oxygen to
form 2 moles of magnesium oxide
Step 4: Use appropriate state symbols in the fully balanced equation
2Mg(s) + O2(g) → 2MgO(s)

Answer 1:
Step 1: To balance the equation, write out the symbol equation showing reactants and products
Zn + CuSO4 → ZnSO4 + Cu
Step 2: Count the numbers of atoms in each reactant and product. The equation is already
balanced

Step 3: Use appropriate state symbols in the equation

Zn (s) + CuSO4 (aq) → ZnSO4 (aq) + Cu (s)
Answer 2:
Step 1: The full chemical equation for the reaction is
 Zn (s) + CuSO4 (aq) → ZnSO4 (aq) + Cu (s)
Step 2: Break down reactants into their respective ions
Zn (s) + Cu2+ SO42- (aq) → Zn2+SO42- (aq) + Cu (s)
Step 3: Cancel the spectator ions on both sides to give the ionic equation
Zn (s) + Cu2+SO42- (aq) → Zn2+SO42- (aq) + Cu (s)
Zn (s) + Cu2+(aq) → Zn2+ (aq) + Cu (s)
2.3Formulae
Empirical & Molecular Formulae
• The molecular formula is the formula that shows the number and type of each atom in
a molecule
o Eg. the molecular formula of ethanoic acid is C2H4O2
• The empirical formula is the simplest whole number ratio of the elements present in one
molecule or formula unit of the compound
o Eg. the empirical formula of ethanoic acid is CH2O
• Organic molecules often have different empirical and molecular formulae
• Simple inorganic molecules however have often similar empirical and molecular
formulae
• Ionic compounds always have similar empirical and molecular formulae

Empirical & Molecular Formulae Calculations

Empirical formula
• Empirical formula is the simplest whole number ratio of the elements present in one
molecule or formula unit of the compound
• It is calculated from knowledge of the ratio of masses of each element in the compound
• The empirical formula can be found by determining the mass of each element present in
a sample of the compound
• It can also be deduced from data that give the percentage compositions by mass of the
elements in a compound

Worked Example: Empirical formula from mass

Worked Example 2: Empirical formula from %

Molecular formula
• The molecular formula gives the exact numbers of atoms of each element present in the
formula of the compound
• The molecular formula can be found by dividing the relative formula mass of the
molecular formula by the relative formula mass of the empirical formula
• Multiply the number of each element present in the empirical formula by this number to
find the molecular formula
Worked example: Calculating molecular formula

Answer
• Step 1: Calculate relative formula mass of empirical formula
Relative formula mass = (C x 4) + (H x 10) + (S x 1)
Relative formula mass = (12 x 4) + (1 x 10) + (32 x 1)
Relative formula mass = 90
• Step 2: Divide relative formula mass of X by relative formula mass of empirical formula
Ratio between Mr of X and the Mr of the empirical formula = 180/90
Ratio between Mr of X and the Mr of the empirical formula = 2
• Step 3: Multiply each number of elements by 2
(C4 x 2) + (H10 x 2) + (S1 x 2) = (C8) + (H20) + (S2)
Molecular Formula of X is C8H20S2
Water of Crystallisation
• Water of crystallisation is when some compounds can form crystals which have water
as part of their structure
• A compound that contains water of crystallisation is called a hydrated compound
• The water of crystallisation is separated from the main formula by a dot when writing the
chemical formula of hydrated compounds
o Eg. hydrated copper(II) sulfate is CuSO4∙5H2O
• A compound which doesn’t contain water of crystallisation is called an anhydrous
compound
o Eg. anhydrous copper(II) sulfate is CuSO4
• A compound can be hydrated to different degrees
o Eg. cobalt(II) chloride can be hydrated by six or two water molecules
o CoCl2 ∙6H2O or CoCl2 ∙2H2O
• The conversion of anhydrous compounds to hydrated compounds is reversible by
heating the hydrated salt
Anhydrous to hydrated salt:
CuSO4 + 5H2O → CuSO4∙5H2O
Hydrated to anhydrous salt (by heating):
CuSO4∙5H2O → CuSO4 + 5H2O
2.4Reacting masses and volumes (of solutions and gases)
Mole Calculations
• The number of moles of a substance can be found by using the following equation:

• It is important to be clear about the type of particle you are referring to when dealing with
moles
o Eg. 1 mole of CaF2 contains one mole of CaF2 formula units, but one mole of
Ca2+ and two moles of F– ions
Reacting masses
• The masses of reactants are useful to determine how much of the reactants exactly react
with each other to prevent waste
• To calculate the reacting masses, the chemical equation is required
• This equation shows the ratio of moles of all the reactants and products, also called the
stoichiometry, of the equation
• To find the mass of products formed in a reaction the following pieces of information is
needed:
o The mass of the reactants
o The molar mass of the reactants
o The balanced equation
Percentage yield
• In a lot of reactions, not all reactants react to form products which can be due to several
factors:
o Other reactions take place simultaneously
o The reaction does not go to completion
o Reactants or products are lost to the atmosphere
 • The percentage yield shows how much of a particular product you get from the reactants
compared to the maximum theoretical amount that you can get:

• Where actual yield is the number of moles or mass of product obtained experimentally
• The predicted yield is the number of moles or mass obtained by calculation
Worked example: Mass calculation using moles

Answer
• Step 1: The symbol equation is:
2Mg(s) + O2(g) → 2MgO(s)
• Step 2: The relative formula masses are:
Magnesium : 24 Oxygen : 32 Magnesium Oxide : 40
• Step 3: Calculate the moles of magnesium used in reaction

• Step 4: Find the ratio of magnesium to magnesium oxide using the balanced chemical
equation

Therefore, 0.25 mol of MgO is formed

• Step 5: Find the mass of magnesium oxide
mass = mol x Mr
mass = 0.25 mol x 40 g mol-1
mass = 10 g
Therefore, mass of magnesium oxide produced is 10 g
Worked Example: Calculate % yield using moles
Answer
• Step 1: The symbol equation is:
Zn (s) + CuSO4 (aq) → ZnSO4 (aq) + Cu (s)
• Step 2: Calculate the amount of zinc reacted in moles

• Step 3: Calculate the maximum amount of copper that could be formed from the molar
ratio:
Since the ratio of Zn(s) to Cu(s) is 1:1 a maximum of 0.10 moles can be produced
• Step 4: Calculate the maximum mass of copper that could be formed (theoretical yield)
mass = mol x Mr
mass = 0.10 mol x 64 g mol-1
mass = 6.4 g
• Step 5: Calculate the percentage yield of copper

Excess & limiting reagents

• Sometimes, there is an excess of one or more of the reactants (excess reagent)
• The reactant which is not in excess is called the limiting reagent
• To determine which reactant is limiting:
o The number of moles of the reactants should be calculated
o The ratio of the reactants shown in the equation should be taken into account eg:
C + 2H2 → CH4
There are 10 mol of Carbon reacting with 3 mol of Hydrogen
• Hydrogen is the limiting reagent and since the ratio of C : H2 is 1:2 only 1.5 mol of C
will react with 3 mol of H2

Worked example: Excess & limiting reagent

Answer
• Step 1: Calculate the moles of each reactant

• Step 2: Write the balanced equation and determine the molar ratio
2Na + S → Na2S
The molar ratio of Na: Na2S is 2:1
• Step 3: Compare the moles and determine the limiting reagent
So to react completely 0.40 moles of Na require 0.20 moles of S and since there are 0.25 moles
of S, then S is in excess. Na is therefore the limiting reactant.
Volumes of gases
• Avogadro suggested that ‘equal volumes of gases contain the same number of
molecules’ (also called Avogadro’s hypothesis)
• At room temperature (20 degrees Celsius) and pressure (1 atm) one mole of any gas has a
volume of 24.0 dm3
• This molar gas volume of 24.0 dm3 can be used to find:
o The volume of a given mass or number of moles of gas:
volume of gas (dm3) = amount of gas (mol) x 24
• The mass or number of moles of a given volume of gas:
Worked example: Calculation volume of gas using excess & limiting reagents

Answer

Volumes & concentrations of solutions

• The concentration of a solution is the amount of solute dissolved in a solvent to make 1
dm3 of solution
o The solute is the substance that dissolves in a solvent to form a solution
o The solvent is often water

• A concentrated solution is a solution that has a high concentration of solute

• A dilute solution is a solution with a low concentration of solute
• When carrying out calculations involve concentrations in mol dm-3 the following points
need to be considered:
o Change mass in grams to moles
o Change cm3 to dm3
 • To calculate the mass of a substance present in solution of known concentration and
volume:
o Rearrange the concentration equation
number of moles (mol) = concentration (mol dm-3) x volume (dm3)
o Multiply the moles of solute by its molar mass
mass of solute (g) = number of moles (mol) x molar mass (g mol-1)
Worked example: Calculating volume from concentration

Answer
• Step 1: Write the balanced symbol equation
CaCO3 + 2HCl → CaCl2 + H2O + CO2
• Step 2: Calculate the amount, in moles, of calcium carbonate that reacts

• Step 3: Calculate the moles of hydrochloric acid required using the reaction’s
stoichiometry
1 mol of CaCO3 requires 2 mol of HCl
So 0.025 mol of CaCO3 requires 0.05 mol of HCl
• Step 4: Calculate the volume of HCl required

Volume of hydrochloric acid = 0.05 dm3

Worked example: Neutralisation calculation

Answer
• Step 1: Write the balanced symbol equation
Na2CO3 + 2HCl → Na2Cl2 + H2O + CO2
• Step 2: Calculate the amount, in moles, of sodium carbonate reacted by rearranging the
equation for amount of substance (mol) and dividing by the volume by 1000 to convert
cm3 to dm3
amount (Na2CO3) = 0.025 dm3 x 0.050 mol dm-3 = 0.00125 mol
• Step 3: Calculate the moles of hydrochloric acid required using the reaction’s
stoichiometry
1 mol of Na2CO3 reacts with 2 mol of HCl, so the molar ratio is 1 : 2
Therefore 0.00125 moles of Na2CO3 react with 0.00250 moles of HCl
• Step 4: Calculate the concentration, in mol dm-3 of hydrochloric acid
Stoichiometric relationships
• The stoichiometry of a reaction can be found if the exact amounts of reactants and
products formed are known
• The amounts can be found by using the following equation:

• The gas volumes can be used to deduce the stoichiometry of a reaction

o Eg. in the combustion of 50 cm3 of propane reacting with 250 cm3 of oxygen, 150
cm3 of carbon dioxide is formed suggesting that the ratio of
propane:oxygen:carbon dioxide is 1:5:3
C3H8 (g) + 5O2 (g) → 3CO2 (g) + H2O (l)

Summary
• Electrons in an atom can exist only in certain energy levels (shells) outside the nucleus.
• The main energy levels (shells) are given principal quantum numbers n = 1, 2, 3, 4, etc. The
lowest energy level (n = 1) is closest to the nucleus.
• The shells may be divided into subshells known as s, p and d subshells, which can hold a
maximum of 2, 6 and 10 electrons, respectively.
• The region of space in which an electron is likely to be found is called an orbital. Each
subshell has a number of orbitals which can each hold a maximum of two electrons. Subshells
s, p and d have 1, 3 and 5 orbitals, respectively.
• The s orbitals are spherical in shape. The p orbitals have two ‘lobes’.
• When two electrons are present in an orbital they spin in opposite directions and are said to be
paired.
• The electronic configuration of atoms is found by adding electrons to each orbital starting
from those in the lowest energy level.
• When electrons are added to orbitals in the same subshell they go into separate orbitals if
possible. Electrons pair up where this is not possible.
• The 1st ionisation energy of an element is the energy needed to remove one electron from each
atom in one mole of atoms of the element in the gaseous state (to form gaseous 1+ ions).
• The ionisation energies needed to remove the first, second, third, fourth, etc., electrons from
each atom or ion in a mole of gaseous atoms are called successive ionisation energies.
• The magnitude of the ionisation energy depends on these four factors:
– the distance of the electron from the nucleus
– the number of positive charges in the nucleus
– the degree of shielding of outer electrons by inner electron shells
– spin-pair repulsion.
• The trends in 1st ionisation energy of the elements across a period and down a group can be
explained using the four factors above.
• Values of successive ionisation energies of atoms provide evidence for their electronic
configuration.
END OF CHAPTER QUESTION
CHAPTER 3
CHEMICAL BONDING
Learning Objectives:
3.1 Electronegativity and bonding
3.2 Ionic bonding
3.3 Metallic bonding
3.4 Covalent bonding and coordinate (dative covalent) bonding
3.5 Shapes of molecules
3.6 Intermolecular forces, electronegativity and bond properties
3.7 Dot-and-cross diagrams

Learning Outcomes:
→ Define electronegativity as the power of an atom to attract electrons to itself
→ Explain the factors influencing the electronegativities of the elements in terms of nuclear charge,
atomic radius and shielding by inner shells and sub-shells
→ State and explain the trends in electronegativity across a period and down a group of the
Periodic Table
→ Use the differences in Pauling electronegativity values to predict the formation of ionic and
covalent bonds (the presence of covalent character in some ionic compounds will not be
assessed) (Pauling electronegativity values will be given where necessary)
→ Define ionic bonding as the electrostatic attraction between oppositely charged ions (positively
charged cations and negatively charged anions)
→ Describe ionic bonding including the examples of sodium chloride, magnesium oxide and
calcium fluoride
→ Define metallic bonding as the electrostatic attraction between positive metal ions and
delocalised electrons
→ Define covalent bonding as electrostatic attraction between the nuclei of two atoms and a shared
pair of electrons
(a) describe covalent bonding in molecules including:
•• hydrogen, H₂
•• oxygen, O₂
•• nitrogen, N₂
•• chlorine, Cl₂
•• hydrogen chloride, HCl
•• carbon dioxide, CO₂
•• ammonia, NH₃
•• methane, CH₄
•• ethane, C₂H6
•• ethene, C2H4
Continued:
b) understand that elements in period 3 can expand their octet including in the compounds
sulfur dioxide, SO₂, phosphorus pentachloride, PCl5 , and sulfur hexafluoride, SF6
(c) describe coordinate (dative covalent) bonding, including in the reaction between ammonia
and hydrogen chloride gases to form the ammonium ion, NH4⁺ , and in the Al 2Cl 6
molecule
→ Describe covalent bonds in terms of orbital overlap giving σ and π bonds:
•• σ bonds are formed by direct overlap of orbitals between the bonding atoms
•• π bonds are formed by the sideways overlap of adjacent p orbitals above and below the σ
bond
→ Describe how the σ and π bonds form in molecules including H2, C2H6, C2H4, HCN and N2
→ Use the concept of hybridisation to describe sp, sp2 and sp3 orbitals
→ Define the terms:
•• bond energy as the energy required to break one mole of a particular covalent bond in the
gaseous state
→ •• bond length as the internuclear distance of two covalently bonded atoms
→ Use bond energy values and the concept of bond length to compare the reactivity of covalent
molecules
→ State and explain the shapes of, and bond angles in, molecules by using VSEPR theory,
including as simple examples:
•• BF3 (trigonal planar, 120°)
•• CO2 (linear, 180°)
•• CH4 (tetrahedral, 109.5°)
•• NH3 (pyramidal, 107°)
•• H2O (non-linear, 104.5°)
•• SF6 (octahedral, 90°)
•• PF5 (trigonal bipyramidal, 120° and 90°)
→ Predict the shapes of, and bond angles in, molecules and ions analogous to those specified in
3.5.1
→ Describe hydrogen bonding, limited to molecules containing N–H and O–H groups,
including ammonia and water as simple examples
→ Use the concept of hydrogen bonding to explain the anomalous properties of H2O (ice and
water):
•• its relatively high melting and boiling points
•• its relatively high surface tension
•• the density of the solid ice compared with the liquid water
→ Use the concept of electronegativity to explain bond polarity and dipole moments of
molecules
→ Describe van der Waals’ forces as the intermolecular forces between molecular entities other
than those due to bond formation, and use the term van der Waals’ forces as a generic term
to describe all intermolecular forces
 Continued:
→ Describe the types of van der Waals’ force:
•• instantaneous dipole – induced dipole (id-id) force, also called London dispersion forces
•• permanent dipole – permanent dipole (pd-pd) force, including hydrogen bonding
→ Describe hydrogen bonding and understand that hydrogen bonding is a special case of
permanent dipole – permanent dipole force between molecules where hydrogen is bonded
to a highly electronegative atom
→ State that, in general, ionic, covalent and metallic bonding are stronger than intermolecular
forces
→ Use dot-and-cross diagrams to illustrate ionic, covalent and coordinate bonding including the
representation of any compounds stated in 3.4 and 3.5 (dot-and-cross diagrams may include
species with atoms which have an expanded octet or species with an odd number of
electrons)

3.1 Electronegativity and Bonding

Electronegativity: Definition
• Electronegativity is the ability of an atom to attract a pair of electrons towards itself in a
covalent bond
• This phenomenon arises from the positive nucleus’s ability to attract the negatively
charged electrons, in the outer shells, towards itself
• The Pauling scale is used to assign a value of electronegativity for each atom

First three rows of the periodic table showing electronegativity values

• Fluorine is the most electronegative atom on the Periodic Table, with a value of 4.0 on
the Pauling Scale
• It is best at attracting electron density towards itself when covalently bonded to another
atom
 Electron distribution in the C-F bond of fluoromethane

Electronegativity: Affecting Factors

Nuclear charge

• Attraction exists between the positively charged protons in the nucleus and negatively
charged electrons found in the energy levels of an atom
• An increase in the number of protons leads to an increase in nuclear attraction for the
electrons in the outer shells
• Therefore, an increased nuclear charge results in an increased electronegativity

As the nuclear charge increases, the electronegativity of an element increases as well

Atomic radius

• The atomic radius is the distance between the nucleus and electrons in the outermost
shell
• Electrons closer to the nucleus are more strongly attracted towards its positive nucleus
• Those electrons further away from the nucleus are less strongly attracted towards the
nucleus
• Therefore, an increased atomic radius results in a decreased electronegativity
 As the atomic radius increases, the nucleus has less of an attraction for the bonding electrons
causing atom A to have a higher electronegativity than atom B

Shielding

• Filled energy levels can shield (mask) the effect of the nuclear charge causing the outer
electrons to be less attracted to the nucleus
• Therefore, the addition of extra shells and subshells in an atom will cause the outer
electrons to experience less of the attractive force of the nucleus
o Sodium (Period 3, Group 1) has higher electronegativity than caesium (Period 6,
Group 1) as it has fewer shells and therefore the outer electrons experience less
shielding than in caesium
• Thus, an increased number of inner shells and subshells will result in a decreased
electronegativity

Filled inner energy levels mask the nuclear attraction from the outer bonding electrons
Electronegativity: Trends
• Electronegativity varies across Periods and down the Groups of the Periodic Table

Down a group

• There is a decrease in electronegativity going down the Group

• The nuclear charge increases as more protons are being added to the nucleus
• However, each element has an extra filled electron shell, which increases shielding
• The addition of the extra shells increases the distance between the nucleus and the outer
electrons resulting in larger atomic radii
• Overall, there is decrease in attraction between the nucleus and outer bonding electrons

Electronegativity decreases going down the groups of the periodic table

Across a period

• Electronegativity increases across a Period

• The nuclear charge increases with the addition of protons to the nucleus
• Shielding remains reasonably the same across the Period as no new shells are being
added to the atoms
• The nucleus has an increasingly strong attraction for the bonding pair of electrons of
atoms across the Period of the Periodic Table
• This results in smaller atomic radii

Electronegativity increases going across the periods of the Periodic Table

Trends down a group & across a period table

3.2 Ionic Bonding

Ionic Bonding: Definition

• As a general rule, metals are on the left of the Periodic Table and nonmetals are on the
right-hand side
• Ionic bonding involves the transfer of electrons from a metallic element to a non-
metallic element
• Transferring electrons usually leaves the metal and the non-metal with a full outer shell
• Metals lose electrons from their valence shell forming positively charged cations
• Non-metal atoms gain electrons forming negatively charged anions
• Once the atoms become ions, their electronic configurations are the same as a stable
noble gas.
o A potassium ion (K+) has the same electronic configuration as argon: [2,8,8]+
o A chloride ion (Cl–) also has the same electronic configuration as argon: [2,8,8]–

Forming cations by the removal of electrons from metals

 Forming anions by the addition of electrons to nonmetals

• Cations and anions are oppositely charged and therefore attracted to each other
• Electrostatic attractions are formed between the oppositely charged ions to form ionic
compounds
• The ionic bond is the electrostatic attraction formed between the oppositely charged
ions, which occurs in all directions
• This form of attraction is very strong and requires a lot of energy to overcome
o This causes high melting points in ionic compounds

Cations and anions bond together using strong electrostatic forces, which require a lot of
energy to overcome
 • The ions form a lattice structure which is an evenly distributed crystalline structure
• Ions in a lattice are arranged in a regular repeating pattern so that positive charges
cancel out negative charges
• The attraction between the cations and anions is occurring in all directions
o Each ion is attracted to all of the oppositely charged ions around it
• Therefore the final lattice is overall electrically neutral

Ionic solids are arranged in lattice structures

Ionic Bonding: Examples

Sodium chloride
• Sodium is a Group 1 metal
o It loses its outer electron to form a sodium ion with a +1 charge (Na+)
• Chlorine is a Group 7 non-metal
o It gains 1 electron to form a chloride ion with a -1 charge (Cl–)
• The oppositely charged ions are attracted to each other by electrostatic forces to form
NaCl (ionic bonds)
• The final ionic solid is neutral in charge

Dot and cross diagram to show the ionic bonding in sodium chloride
Magnesium oxide
• Magnesium is a Group 2 metal
o It loses its 2 outer electrons to form a magnesium ion with a +2 charge (Mg2+)
• Oxygen is a Group 6 non-metal
o It gains 2 electrons to form an oxide ion with a -2 charge (O2-)
• The oppositely charged ions are attracted to each other to by electrostatic forces to form
MgO (ionic bonds)
• The final ionic solid is neutral in charge

Dot and cross diagram to show the ionic bonding in magnesium oxide

Calcium fluoride

• Calcium is a Group 2 metal

o It loses its 2 outer electrons to form a calcium ion with a +2 charge (Ca2+)
• Fluorine is a Group 7 non-metal
o It gains 1 electron to form a fluoride ion with a -1 charge (F–)
• As before, the positive and negative ions are attracted to each other via an ionic bond
• However, to cancel out the 2+ charge of the calcium ion, 2 fluorine atoms are needed
o Each fluorine atom can only accept 1 electron from the calcium atom
o 2 fluoride ions will be formed
• Calcium fluoride is made when 1 calcium ion and 2 fluoride ions form ionic bonds, CaF2
• The final ionic solid of CaF2 is neutral in charge
 Dot and cross diagram to show the ionic bonding in calcium fluoride

Worked example: Dot & cross lithium nitride

Answer
• Lithium is a Group 1 metal
• It loses its outer electron to form a lithium ion with a +1 charge (Li+)
• Nitrogen is a Group 5 non-metal
• It gains 3 electrons to form a nitride ion with a -3 charge (N3-)
• To cancel out the -3 charge of the nitride ion, 3 lithium atoms are needed and 3 lithium
ions will be formed
• Lithium nitride is made when 1 nitride ion and 3 lithium ions form ionic bonds
• The final ionic solid of Li3N is neutral in charge
 Dot and cross diagram to show the ionic bonding in lithium nitride

Worked example: Dot & cross aluminium oxide

Answer
• Aluminium is a Group 3 metal
• It loses its outer electrons to form an aluminium ion with a +3 charge (Al3+)
• Oxygen is a Group 6 non-metal
• It gains 2 electrons to form an oxide ion with a -2 charge (O2-)
• To cancel out the negative and positive charges, 2 aluminium and 3 oxygen atoms are
needed
• Aluminium oxide is made when 2 aluminium ions and 3 oxygen ions form ionic bonds
• The final ionic solid of Al2O3 is neutral in charge

Dot and cross diagram to show the ionic bonding in aluminium oxide
3.3 Metallic Bonding

Metallic Bonding: Definition

• Metal atoms are tightly packed together in lattice structures

• When the metal atoms are in lattice structures, the electrons in their outer shells are free
to move throughout the structure
• The free-moving electrons are called ‘delocalised electrons’ and they are not bound to
their atom
• When the electrons are delocalised, the metal atoms become positively charged
• The positive charges repel each other and keep the neatly arranged lattice in place
• There are very strong forces between the positive metal centres and the ‘sea’ of
delocalised electrons

The positive metal centres are suspended in a ‘sea’ of delocalised electrons

• The strength of the metallic attraction can be increased by:

o Increasing the number of delocalised electrons per metal atom
o Increasing the positive charges on the metal centres in the lattice
o Decreasing the size of the metal ions
3.4 Covalent Bonding and Coordinate (Dative Covalent) Bonding
Covalent Bonding: Definition & Examples
• Covalent bonding occurs between two nonmetals
• A covalent bond involves the electrostatic attraction between nuclei of two atoms and
the bonding electrons of their outer shells
• No electrons are transferred but only shared in this type of bonding

The positive nucleus of each atom has an attraction for the bonding electrons shared in the
covalent bond
• Non-metals are able to share pairs of electrons to form different types of covalent bonds
• Sharing electrons in the covalent bond allows each of the 2 atoms to achieve an electron
configuration similar to a noble gas
o This makes each atom more stable

Covalent bonds & shared electrons table

Dot & cross diagrams

• Dot and cross diagrams are used to represent covalent bonding

• They show just the outer shell of the atoms involved
• To differentiate between the two atoms involved, dots for electrons of one atom and
crosses for electrons of the other atom are used
• Electrons are shown in pairs on dot-and-cross diagrams
Single covalent bonding
Hydrogen, H2

Covalent bonding in hydrogen

Chlorine, Cl2

Covalent bonding in chlorine

Hydrogen Chloride, HCl

Covalent bonding in hydrogen chloride

Ammonia, NH3

Covalent bonding in ammonia

Methane, CH4

Covalent bonding in methane

Ethane, C2H6

Covalent bonding in ethane

Double covalent bonding

Oxygen, O2

Covalent bonding in oxygen

Carbon dioxide, CO2

Covalent bonding in carbon dioxide

Ethene, C2H4

Covalent bonding in ethene

Triple covalent bonding

Nitrogen, N2

Covalent bonding in nitrogen

• In some instances, the central atom of a covalently bonded molecule can accommodate
more or less than 8 electrons in its outer shell
• Being able to accommodate more than 8 electrons in the outer shell is known as
‘expanding the octet rule’
• Accommodating less than 8 electrons in the outer shell means than the central atom is
‘electron deficient’
• Some examples of this occurring can be seen with Period 3 elements

Sulfur dioxide, SO2 – dot and cross diagram

 Phosphorus pentachloride, PCl5 – dot and cross diagram

Sulfur hexafluoride, SF6 – dot and cross diagram

Exam Tip

Covalent bonding takes place between nonmetal atoms.

Remember to use the Periodic Table to decide how many electrons are in the outer shell of a
nonmetal atom.
Coordinate Bonding
Dative Bonding: Definition & Examples
• In simple covalent bonds the two atoms involved shares electrons
• Some molecules have a lone pair of electrons that can be donated to form a bond with an
electron-deficient atom
o An electron-deficient atom is an atom that has an unfilled outer orbital
• So both electrons are from the same atom
• This type of bonding is called dative covalent bonding or coordinate bond
• An example of a dative bond is in an ammonium ion
o The hydrogen ion, H+ is electron-deficient and has space for two electrons in its
shell
o The nitrogen atom in ammonia has a lone pair of electrons which it can donate to
the hydrogen ion to form a dative covalent bond

Ammonia (NH3) can donate a lone pair to an electron-deficient proton (H+) to form a charged
ammonium ion (NH4+)
• Aluminium chloride is also formed using dative covalent bonding
• At high temperatures aluminium chloride can exist as a monomer (AlCl3)
o The molecule is electron-deficient and needs to electrons complete the aluminium
atom’s outer shell
• At lower temperatures the two molecules of AlCl3 join together to form a dimer
(Al2Cl6)
o The molecules combine because lone pairs of electrons on two of the chlorine
atoms form two coordinate bonds with the aluminium atoms
 Aluminium chloride is also formed with a dative covalent bond in which two of the chlorine
atoms donate their lone pairs to each of the aluminium atoms to form a dimer

Covalent Bonding: Orbitals & Hybridisation

Bond overlap in covalent bonds

• A single covalent bond is formed when two nonmetals combine
• Each atom that combines has an atomic orbital containing a single unpaired electron
• When a covalent bond is formed, the atomic orbitals overlap to form a combined
orbital containing two electrons
o This new orbital is called the molecular orbital
• The greater the atomic orbital overlap, the stronger the bond
• Sigma (σ) bonds are formed by direct overlap of orbitals between the bonding atoms
• Pi (π) bonds are formed by the sideways overlap of adjacent above and below the σ
bond

σ bonds
• Sigma (σ) bonds are formed from the end-on overlap of atomic orbitals
• S orbitals overlap this way as well as p orbitals

Sigma orbitals can be formed from the end-on overlap of s orbitals

 • The electron density in a σ bond is symmetrical about a line joining the nuclei of the
atoms forming the bond
• The pair of electrons is found between the nuclei of the two atoms
• The electrostatic attraction between the electrons and nuclei bonds the atoms to each
other

π bonds
• Pi (π) bonds are formed from the sideways overlap of adjacent p orbitals
• The two lobes that make up the π bond lie above and below the plane of the σ bond
• This maximises overlap of the p orbitals
• A single π bond is drawn as two electron clouds one arising from each lobe of the p
orbitals
• The two clouds of electrons in a π bond represent one bond containing two electrons

π orbitals can be formed from the end-on overlap of p orbitals

Examples of sigma & pi bonds

• Hydrogen
o The hydrogen atom has only one s orbital
o The s orbitals of the two hydrogen atoms will overlap to form a σ bond

Direct overlap of the 1s orbitals of the hydrogen atoms results in the formation of a σ bond
• Ethene
o Each carbon atom uses three of its four electrons to form σ bonds
o Two σ bonds are formed with the hydrogen atoms
o One σ bond is formed with the other carbon atom
o The fourth electron from each carbon atom occupies a p orbital which overlaps
sideways with another p orbital on the other carbon atom to form a π bond
o This means that the C-C is a double bond: one σ and one π bond
 Overlap of the p orbitals results in the forming of a π bond in ethene

Each carbon atom in ethene forms two sigma bonds with hydrogen atoms and one σ bond with
another carbon atom. The fourth electron is used to form a π bond between the two carbon atoms

• Ethyne
o This molecule contains a triple bond formed from two π bonds (at right angles to
each other) and one σ bond
o Each carbon atom uses two of its four electrons to form σ bonds
o One σ bond is formed with the hydrogen atom
o One σ bond is formed with the other carbon atom
o Two electrons are used to form two π bonds with the other carbon atom

Ethyne has a triple bond formed from two π bonds and one σ bond between the two carbon
atoms
 • Hydrogen cyanide
o Hydrogen cyanide contains a triple bond
o One σ bond is formed between the H and C atom (overlap of an sp C hybridised
orbital with the 1s H orbital)
o A second σ bond is formed between the C and N atom (overlap of an sp C
hybridised orbital with a p orbital of N)
o The remaining two sets of p orbitals of nitrogen and carbon will overlap to form
two π bonds at right angles to each other

Hydrogen cyanide has a triple bond formed from the overlap of two sets of p orbitals of nitrogen
and carbon and the overlap of an sp hybridised carbon orbital and a p orbital on the nitrogen
• Nitrogen
o Nitrogen too contains a triple bond
o The triple bond is formed from the overlap of the s orbitals on each N to form a σ
bond and the overlap of two sets of p orbitals on the nitrogen atoms to form two
π bonds
o These π bonds are at right angles to each other

The triple bond is formed from two π bonds and one σ bond

Hybridisation

• The p atomic orbitals can also overlap end-on to form σ bonds

• In order for them to do this, they first need to become modified in order to gain s orbital
character
• The orbitals are therefore slightly changed in shape to make one of the p orbital lobe
bigger
• This mixing of atomic orbitals to form covalent bonds is called hybridisation
o Mixing an s with three p orbitals is called sp3 hybridisation (each orbital has ¼ s
character and ¾ p character)
o Mixing an s with tw p orbital is called sp2 hybridisation
o And mixing an s with one p-type orbitals formssp hybridised orbitals

π orbitals can be formed from the end-on overlap of p orbitals

The mixing of s orbitals with p orbitals to form molecular bonds is called hybridisation
Covalent Bonding: Bond Energy & Length

Bond energy
• The bond energy is the energy required to break one mole of a particular covalent bond
in the gaseous states
o Bond energy has units of kJ mol-1
• The larger the bond energy, the stronger the covalent bond is

Bond length
• The bond length is internuclear distance of two covalently bonded atoms
o It is the distance from the nucleus of one atom to another atom which forms the
covalent bond
• The greater the forces of attraction between electrons and nuclei, the more the atoms are
pulled closer to each other
• This decreases the bond length of a molecule and increases the strength of the covalent
bond
• Triple bonds are the shortest and strongest covalent bonds due to the large electron
density between the nuclei of the two atoms
• This increase the forces of attraction between the electrons and nuclei of the atoms
• As a result of this, the atoms are pulled closer together causing a shorter bond length
• The increased forces of attraction also means that the covalent bond is stronger

Triple bonds are the shortest covalent bonds and therefore the strongest ones

Reactivity of covalent molecules

• The reactivity of a covalent bond is greatly influenced by:
o The bond polarity
o The bond strength
o The bond type (σ/π)
Worked example: Bond lengths & bond energies

Answer
Answer 1: Going down the halogen group, the atoms are bigger; the attractive force between the
bonding electrons and the nucleus get smaller so less energy is needed to break the atom
Answer 2: Going down the group the increase in bond length is approximately 0.14-0.20 nm
Fluorine is smaller than HCl, so a value between 0.09 and 0.11 nm is acceptable for the bond
length
Answer 3: The hydrogen halide with the longest bond length and therefore smallest bond energy
is the most reactive as it takes the least energy to break apart the hydrogen and halide atoms apart
Therefore, HI is the most reactive hydrogen halide

3.5 Shapes of Molecules

VSEPR: Theory & Predictions
• The valence shell electron pair repulsion theory (VSEPR) predicts the shape and bond
angles of molecules
• Electrons are negatively charged and will repel other electrons when close to each other
• In a molecule, the bonding pair of electrons will repel other electrons around the
central atom forcing the molecule to adopt a shape in which these repulsive forces are
minimised
• When determining the shape and bond angles of a molecule, the following VSEPR rules
should be considered:
o Valence shell electrons are those electrons that are found in the outer shell
o Electron pairs repel each other as they have similar charges
o Lone pair electrons repel each other more than bonded pairs
o Repulsion between multiple and single bonds is treated the same as for repulsion
between single bonds
o Repulsion between pairs of double bonds are greater
 o The most stable shape is adopted to minimize the repulsion forces
• Different types of electron pairs have different repulsive forces
o Lone pairs of electrons have a more concentrated electron charge cloud than
bonding pairs of electrons
o The cloud charges are wider and closer to the central atom’s nucleus
o The order of repulsion is therefore: lone pair – lone pair > lone pair – bond pair >
bond pair – bond pair

Different types of electron pairs have different repulsive forces

• Molecules can adapt the following shapes and bond angles:

Molecules of different shapes can adapt with their corresponding bond angles
Examples
Examples of molecules with different shapes and bond angles
Worked example: VSEPR & shapes of molecules

Answer 1

Answer 2
Answer 3

Hydrogen Bonding

Hydrogen bonding

• Hydrogen bonding is the strongest form of intermolecular bonding

o Intermolecular bonds are bonds between molecules
o Hydrogen bonding is a type of permanent dipole – permanent dipole bonding
• For hydrogen bonding to take place the following is needed:
o A species which has an O or N (very electronegative) atom with an available
lone pair of electrons
o A species with an -OH or -NH group
• When hydrogen is covalently bonded to an electronegative atom, such as O or N, the
bond becomes very highly polarised
• The H becomes so δ+ charged that it can form a bond with the lone pair of an O or N
atom in another molecule

The electronegative atoms O or N have a stronger pull on the electrons in the covalent bond with
hydrogen, causing the bond to become polarised
 • For hydrogen bonding to take place, the angle between the -OH/-NH and the hydrogen
bond is 180o
• The number of hydrogen bonds depends on:
o The number of hydrogen atoms attached to O or N in the molecule
o The number of lone pairs on the O or N

Ammonia can form a maximum of one hydrogen bond per molecule

Water can form a maximum of two hydrogen bonds per molecule

Properties of water

• Hydrogen bonding in water, causes it to have anomalous properties such as high

melting and boiling points, high surface tension and anomalous density of ice compared
to water

High melting & boiling points

• Water has high melting and boiling points which is caused by the strong
intermolecular forces of hydrogen bonding between the molecules
• In ice (solid H2O) and water (liquid H2O) the molecules are tightly held together by
hydrogen bonds
• A lot of energy is therefore required to break the water molecules apart and melt or boil
them
 Hydrogen bonds are strong intermolecular forces which are difficult to break causing water to
have high melting and boiling points
• The graph below compares the enthalpy of vaporisation (energy required to boil a
substance) of different hydrides
• The enthalpy changes increase going from H2S to H2Te due to the increased number of
electrons in the Group 16 elements
• This causes an increased instantaneous dipole – induced dipole forces as the
molecules become larger
• Based on this, H2O would have a much lower enthalpy change (around 17 kJ mol-1)
• However, the enthalpy change of vaporisation is almost 3 times larger which is caused
by the hydrogen bonds present in water but not in the other hydrides

The high enthalpy change of evaporation of water suggests that instantaneous dipole-induced
dipole forces are not the only forces present in the molecule – there are also those of the strong
hydrogen bonds, which cause the high boiling points

High surface tension

• Water has a high surface tension

• Surface tension is the ability of a liquid surface to resist any external forces (i.e. to stay
unaffected by forces acting on the surface)
• The water molecules at the surface of liquid are bonded to other water molecules through
hydrogen bonds
• These molecules pull downwards on the surface molecules causing the surface them to
become compressed and more tightly together at the surface
• This increases water’s surface tension
 The surface molecules are pulled downwards due to the hydrogen bonds with other molecules,
whereas the inner water molecules are pulled in all directions

Density

• Solids are denser than their liquids as the particles in solids are more closely packed
together than in their liquid state
• In ice however, the water molecules are packed in a 3D hydrogen-bonded network in a
rigid lattice
• Each oxygen atom is surrounded by hydrogen atoms
• This way of packing the molecules in a solid and the relatively long bond lengths of the
hydrogen bonds means that the water molecules are slightly further apart than in the
liquid form
• Therefore, ice has a lower density than liquid water

The ‘more open’ structure of molecules in ice causes it to have a lower density than liquid water
Polarity & Dipole Moments
• Electronegativity is the ability of an atom to draw a pair of electrons towards itself in a
covalent bond
• Electronegativity increases across a Period and decreases going down a Group
Polarity

• When two atoms in a covalent bond have the same electronegativity the covalent bond
is nonpolar

The two chlorine atoms have similar electronegativities so the bonding electrons are shared
equally between the two atoms
• When two atoms in a covalent bond have different electronegativities the covalent bond
is polar and the electrons will be drawn towards the more electronegative atom
• As a result of this:
o The negative charge centre and positive charge centre do not coincide with each
other
o This means that the electron distribution is asymmetric
o The less electronegative atom gets a partial charge of δ+ (delta positive)
o The more electronegative atom gets a partial charge of δ- (delta negative)
• The greater the difference in electronegativity the more polar the bond becomes

Cl has a greater electronegativity than H causing the electrons to be more attracted towards the
Cl atom which becomes delta negative and the H delta positive

Dipole moment

• The dipole moment is a measure of how polar a bond is

• The direction of the dipole moment is shown by the following sign in which the arrow
points to the partially negatively charged end of the dipole:

The sign shows the direction of the dipole moment and the arrow points to the delta negative end
of the dipole
Assigning polarity to molecules

• To determine whether a molecule with more than two atoms is polar, the following
things have to be taken into consideration:
o The polarity of each bond
o How the bonds are arranged in the molecule
• Some molecules have polar bonds but are overall not polar because the polar bonds in
the molecule are arranged in such way that the individual dipole moments cancel each
other out

There are four polar covalent bonds in CH3Cl which do not cancel each other out causing
CH3Cl to be a polar molecule; the overall dipole is towards the electronegative chlorine atom

Though CCl4 has four polar covalent bonds, the individual dipole moments cancel each other out
causing CCl4 to be a nonpolar molecule

van der Waals' Forces & Dipoles

• Covalent bonds are strong intramolecular forces
• Molecules also contain weaker intermolecular forces which are forces between
molecules
• These intermolecular forces are called van der Waals’ forces
• There are two types of van der Waals’ forces:
o Instantaneous (temporary) dipole – induced dipole forces also called London
dispersion forces
 o Permanent dipole – permanent dipole forces

The polar covalent bonds between O and H atoms are intramolecular forces and the permanent
dipole – permanent dipole forces between the molecules are intermolecular forces as they are a
type of van der Waals’ force

Instantaneous dipole – induced dipole (id – id)

• Instantaneous dipole – induced dipole forces or London dispersion forces exist

between all atoms or molecules
• The electron charge cloud in non-polar molecules or atoms are constantly moving
• During this movement, the electron charge cloud can be more on one side of the atom or
molecule than the other
• This causes a temporary dipole to arise
• This temporary dipole can induce a dipole on neighbouring molecules
• When this happens, the δ+ end of the dipole in one molecule and the δ- end of the
dipole in a neighbouring molecule are attracted towards each other
• Because the electron clouds are moving constantly, the dipoles are only temporary

Id-id (London dispersion) forces between two non-polar molecules

 • Id – id forces increase with:
o Increasing number of electrons (and atomic number) in the molecule
o Increasing the places where the molecules come close together

Going down the Group, the id-id forces increase due to the increased number of electrons in the
atoms

The increased number of contact points in petane means that it has more id-id forces and
therefore a higher boiling point

Permanent dipole – permanent dipole (pd – pd)

• Polar molecules have permanent dipoles

• The molecule will always have a negatively and positively charged end
• Forces between two molecules that have permanent dipoles are called permanent dipole
– permanent dipole forces
• The δ+ end of the dipole in one molecule and the δ- end of the dipole in a neighbouring
molecule are attracted towards each other

The delta negative end of one polar molecule will be attracted onwards the delta positive end of
a neighbouring polar molecule
 • For small molecules with the same number of electrons, pd – pd forces are stronger
than id – id
o Butane and propanone have the same number of electrons
o Butane is a nonpolar molecule and will have id – id forces
o Propanone is a polar molecule and will have pd – pd forces
o Therefore, more energy is required to break the intermolecular forces between
propanone molecules than between butane molecules
o So, propanone has a higher boiling point than butane

Pd-pd forces are stronger than id-id forces in smaller molecules with an equal number of
electrons
Hydrogen Bonding as a Permanent Dipole
• Hydrogen bonding is an intermolecular force between molecules with an -OH/-NH
group and molecules with an N/O atom
• Hydrogen bonding is a special case of a permanent dipole – dipole force between
molecules
o Hydrogen bonds are stronger forces than pd – pd forces
• The hydrogen is bonded to an O/N atom which is so electronegative, that almost all the
electron density from the covalent bond is drawn towards the O/N atom
• This leaves the H with a large delta positive and the O/N with a large delta negative
charging resulting in the formation of a permanent dipole in the molecule
• A delta positive H in one molecule is electrostatically attracted to the delta negative
O/N in a neighbouring molecule

Hydrogen bonds in water molecules

3.6 Intermolecular Forces, Electronegativity and Bond Properties

Comparing Bonds to Intermolecular Forces

Intramolecular forces
• Intramolecular forces are forces within a molecule
• Ionic bonding is the electrostatic attraction between positive (cations) and negative
(anions) ions in an ionic crystal lattice
o These ions are formed by transferring the electrons from one species to the other
• Covalent bonds are formed when the outer electrons of two atoms are shared
• Metallic bonding is the electrostatic attraction of positively charged metal ions and
their delocalised electrons in a metal lattice

Intramolecular forces

Intermolecular forces

• Intermolecular forces are forces between molecules and are also called van der Waals’
forces
• Permanent dipole – permanent dipole are the attractive forces between two
neighbouring molecules with a permanent dipole
• Hydrogen bonds are a special type of permanent dipole – permanent dipole forces
• Instantaneous dipole – induced dipole (London dispersion) forces are the attractive
forces between a temporary dipole and a neighbouring molecule with an induced dipole
 Intermolecular forces
• In general, the intramolecular forces are stronger than intermolecular forces
• The strengths of the types of bond or force are as follows:

The varying strengths of different types of bonds

3.7 Dot-and-Cross Diagrams

Dot & Cross Diagrams
• Dot and cross diagrams are diagrams that show the arrangement of the outer-shell
electrons in an ionic or covalent compound or element
o The electrons are shown as dots and crosses
• In a dot and cross diagram:
o Only the outer electrons are shown
o The charge of the ion is spread evenly which is shown by using brackets
o The charge on each ion is written at the top right-hand corner
Ionic compounds

• Ionic bonds are formed when metal transfer electrons to a non-metal to form a positively
charged and negatively charged ion
• The atoms achieve a noble gas configuration

Dot-and-cross diagrams of ionic compounds in which one of the atoms transfers their valence
electrons to the other

Covalent compounds

• The atoms in covalent compounds will share their outer valence electrons to achieve a
noble gas configuration
Dot-and-cross diagrams of covalent compounds in which the atoms share their valence electrons
Coordinate bonding

• Coordinate bonding or also called dative covalent bonding is formed when one atom
provides both the electrons needed for a covalent bond
• In a displayed formula, the dative covalent bond is represented by an arrow
• The head of the arrow points away from the lone pair that forms the bond

Dot-and-cross diagrams of dative covalent compounds in which one of the atoms provides both
the electrons in a covalent bond

Incomplete & expanded octet rule

• Some species may contain more (expanded) or less (incomplete) than eight electrons in
their outer shell
Expanded octet rule
 Incomplete octet rule

Odd number of electrons

• Some atoms in compounds may have an odd number of electrons in their valence shell

Incomplete octet rule

Summary
• Ions are formed when atoms gain or lose electrons.
• Ionic (electrovalent) bonding involves an attractive force between positively and negatively
• charged ions in an ionic lattice.
• A covalent bond is formed when atoms share a pair of electrons.
• When atoms form covalent or ionic bonds each atom or ion has a full outer electron shell of
electrons. (Some covalent compounds may be electron deficient or have an ‘expanded
octet’.)
• Dot-and-cross diagrams can be drawn to show the arrangement of electrons in ionic and
covalent compounds.
• In dative covalent bonding one atom provides both electrons in the formation of the
covalent bond.
• The shapes and bond angles in molecules can be predicted using the idea that lone pairs of
electrons repel other lone pairs more than bond pair electrons, and that bond pair to bond
pair repulsion is least.
• σ bonds (sigma bonds) are formed by end-on overlap of atomic orbitals, whereas π bonds
(pi bonds) are formed by sideways overlap of p-type atomic orbitals.
• Three types of relatively weak intermolecular forces are hydrogen bonding, permanent
dipole–dipole forces and van der Waals’ forces.
• Electronegativity differences can be used to predict the type of weak intermolecular forces
between molecules.
Continued
• Hydrogen bonding occurs between molecules that have a hydrogen atom covalently bonded
to an atom of a very electronegative element (fluorine, oxygen or nitrogen).
• The reactivities of covalent bonds can be explained in terms of bond energy, bond length and
bond polarity.
• Intermolecular forces are based on either permanent dipoles, as in CHCl3(l), or temporary
induced dipoles (van der Waals’ forces), as in Br2(l).
• Metallic bonding can be explained in terms of a lattice of positive ions surrounded by mobile
electrons.
• The physical properties of substances may be predicted from the type of bonding present.
• Substances with ionic bonding have high melting and boiling points, whereas simple
molecules with covalent bonding have low melting points.
• The presence of hydrogen bonding in a molecule influences its melting point and boiling
point.
CHAPTER 4
STATES OF MATTER
Learning Objectives:
4.1 The gaseous state: ideal and real gases and pV = nRT
4.2 Bonding and structure

Learning Outcomes:
Candidates should be able to:

→ Explain the origin of pressure in a gas in terms of collisions between gas molecules and the wall
of the container
→ Understand that ideal gases have zero particle volume and no intermolecular forces of attraction
→ State and use the ideal gas equation pV = nRT in calculations, including in the determination of
Mr
→ Describe, in simple terms, the lattice structure of a crystalline solid which is:
(a) giant ionic, including sodium chloride and magnesium oxide
(b) simple molecular, including iodine, buckminsterfullerene C60 and ice
(c) giant molecular, including silicon (IV) oxide, graphite and diamond
(d) giant metallic, including copper
→ Describe, interpret and predict the effect of different types of structure and bonding on the
physical properties of substances, including melting point, boiling point, electrical conductivity
and solubility
→ Deduce the type of structure and bonding present in a substance from given information
 INTRODUCTION:
In the last topic we learn how atoms bond together covalently to form molecules. We
finished that topic with a brief look at how the molecules themselves might attract one another.
In this topic we examine how these attraction between molecules and between other
particles, can help to explain the differences between solids, liquids and gases. We explore the
giant structures that atoms and ions can form, in which it is impossible to say where one
structural unit finishes and the next one starts. We then take a closer look at gases, and see
how the simple assumptions of the kinetic theory of gases lead us to the ideal gas equation,
pV=nRT. Finally we see how the behaviour or real gases can differ markedly from that of an
ideal gas.

The three states of water are ice, water and steam. The ‘steam’ we see from the kettle is
condensed droplets of water. The real gaseous water is in the area between this condensation
and the spout of the kettle. We can’t see it because it is colourless
 4.1The gaseous state: ideal and real gases and pV = nRT
States of Matter
Gases have no fixed shape or volume. Gas particles:
 are far apart, therefore gases can be compressed
 are randomly arranged
 can move freely from place to place, in all directions.
Liquids take the shape of the container they occupy. Liquid particles:
 are close together, so liquids have a fixed volume and can only be compressed
slightly
 are arranged fairly randomly
 have limited movement from place to place, in all directions.
Solids have a fixed shape and volume. Solid particles:
 are touching each other, so solids cannot be compressed
 are usually in a regular arrangement
 cannot change positions with each other – they can only vibrate.
Gases: Gas Pressure
• Gases in a container exert a pressure as the gas molecule are constantly colliding with
the wall of the container

Gas particles exert a pressure by constantly colliding with the walls of the container
Changing gas volume
• Decreasing the volume (at constant temperature) of the container causes the molecules to
be squashed together which results in more frequent collisions with the container wall
• The pressure of the gas increases
• The volume is therefore inversely proportional to the pressure (at constant
temperature)
o A graph of volume of gas plotted against 1/pressure gives a straight line

Decreasing the volume of a gas causes an increased collision frequency of the gas particles
with the container wall (a); volume is inversely proportional to the pressure (b)
Changing gas temperature
• Increasing the temperature (at constant volume) of the gas causes the molecules to gain
more kinetic energy
• This means that the particles will move faster and collide with the container walls more
frequently
• The pressure of the gas increases
• The temperature is therefore directly proportional to the pressure (at constant
volume)
o A graph of temperature of gas plotted against pressure gives a straight line
 Increasing the temperature of a gas causes an increased collision frequency of the gas
particles with the container wall (a); temperature is directly proportional to the pressure (b)

Gases: Ideal Gas Law & Equation

Kinetic theory of gases
• The kinetic theory of gases states that molecules in gases are constantly moving
• The theory makes the following assumptions:
o The gas molecules are moving very fast and randomly
o The molecules hardly have any volume
o The gas molecules do not attract or repel each other (no intermolecular forces)
o No kinetic energy is lost when the gas molecules collide with each other (elastic
collisions)
o The temperature of the gas is related to the average kinetic energy of the
molecules
• Gases that follow the kinetic theory of gases are called ideal gases
• However, in reality gases do not fit this description exactly but may come very close and
are called real gases
Ideal gases
• The volume that an ideal gas occupies depends on:
o Its pressure
o Its temperature
o See section Changing gas volume of page Gas Pressure
• When a gas is heated (at constant pressure) the particles gain more kinetic energy and
undergo more frequent collisions with the container wall
• To keep the pressure constant, the molecules must get further apart and therefore the
volume increases
• The volume is therefore directly proportional to the temperature (at constant pressure)
The volume of a gas increases upon heating to keep a constant pressure (a); volume is directly
proportional to the pressure (b)
Limitations of the ideal gas law
• At very high temperatures and pressures real gases do not obey the kinetic theory as
under these conditions:
o Molecules are close to each other
o There are instantaneous dipole- induced dipole or permanent dipole- permanent
dipole forces between the molecules
o These attractive forces pull the molecules away from the container wall
o The volume of the molecules is not negligible
• Real gases therefore do not obey the following kinetic theory assumptions at high
temperatures and pressures:
o There is zero attraction between molecules (due to attractive forces, the pressure
is lower than expected for an ideal gas)
o The volume of the gas molecules can be ignored (volume of the gas is smaller
than expected for an ideal gas)
Ideal gas equation
• The ideal gas equation shows the relationship between pressure, volume, temperature
and number of moles of gas of an ideal gas:
pV = nRT
p = pressure (pascals, Pa)
V = volume (m3)
n = number of moles of gas (mol)
R = gas constant (8.31 J K-1 mol-1)
T = temperature (kelvin, K)
• The ideal gas equation can also be used to calculate the molar mass (Mr) of a gas
Worked example: Calculating the volume of a gas

Answer
• Step 1: Rearrange the ideal gas equation to find volume of gas

• Step 2: Calculate the volume the oxygen gas occupies

p = 220 kPa = 220 000 Pa
n = 0.781 mol
R = 8.31 J K-1 mol-1
T = 21 oC = 294 K

= 0.00867 m3
= 8.67 dm3
Worked example: Calculating the molar mass of a gas

Answer
• Step 1: Rearrange the ideal gas equation to find the number of moles of gas

• Step 2: Calculate the number of moles of gas

p = 300 kPa = 300 000 Pa
V = 1 dm3 = 0.001 m3
R = 8.31 J K-1 mol-1
T = 23 oC = 296 K

• Step 3: Calculate the molar mass using the number of moles of gas

Exam Tip
Ideal gases have zero particle volume (the particles are really small) and no intermolecular
forces of attraction or repulsion.
To calculate the temperature in Kelvin, add 273 to the Celsius temperature, eg. 100 oC is 373
Kelvin. Remember: an ideal gas will have a volume that is directly proportional to the
temperature and inversely proportional to the pressure.
Lattice Structures
• Most ionic, metallic and covalent compounds are crystalline lattice
• The ions, atoms or molecules are arranged in a regular and repeating arrangement
Giant ionic lattices
• An ionic bond is an electrostatic force between a positively charged metal (cation) ion
and a negatively charged non-metal (anion) ion
o The metal becomes positively charged as it transfers electrons to the non-metal
becomes negatively charged
• Ionic compounds are arranged in giant ionic lattices (also called giant ionic structures)
• The type of lattice formed depends on the sizes of the positive and negative ions which
are arranged in an alternating fashion
o The ionic lattice of MgO and NaCl are cubic

Ionic lattices of the ionic compounds NaCl and MgO

General ionic lattice which shown the actual packing of the ions
Covalent lattices
• Covalent bonds are bonds between nonmetals in which electrons are shared between the
atoms
• Covalent compounds can be arranged in simple molecular or giant molecular lattices
o Simple molecular lattices: Iodine, buckminsterfullerene (C60) and ice
o Giant molecular: silicon(IV) oxide, graphite and diamond
Simple molecular lattices

Giant molecular lattices

Metallic lattices
• Metals form giant metallic lattices in which the metal ions are surrounded by a ‘sea’ of
delocalised electrons
• The metal ions are often packed in hexagonal layers or in a cubic arrangement

Layers of copper ions (the delocalised electrons are not shown in the diagram)

4.2 Bonding and structure

Effects of Bonding & Structure on Physical Properties

• Different types of structure and bonding have different effects on the physical
properties of substances such as their melting and boiling points, electrical
conductivity and solubility
Ionic bonding & giant ionic lattice structures
• Ionic compounds are strong
o The strong electrostatic forces in ionic compounds keep the ions strongly
together
• They are brittle as ionic crystals can split apart
• Ionic compounds have high melting and boiling points
o The strong electrostatic forces between the ions in the lattice act in all directions
and keep them strongly together
o Melting and boiling points increase with charge density of the ions due to the
greater electrostatic attraction of charges
o Mg2+O2- has a higher melting point Na+Cl–
• Ionic compounds are soluble in water as they can form ion – dipole bonds
• Ionic compounds only conduct electricity when molten or in solution
o When molten or in solution, the ions can freely move around and conduct
electricity
o In the solid state they’re in a fixed position and unable to move around
Metallic bonding & giant metallic lattice structures
• Metallic compounds are malleable
o When a force is applied, the metal layers can slide
o The attractive forces between the metal ions and electrons act in all directions
 o So when the layers slide, the metallic bonds are re-formed
o The lattice is not broken and has changed shape
• Metallic compounds are strong and hard
o Due to the strong attractive forces between the metal ions and delocalised
electrons
• Metals have high melting and boiling points
• Pure metals are insoluble in water
• Metals can conduct electricity when in the solid or liquid state
o As both in the solid and liquid state there are mobile electrons which can freely
move around and conduct electricity

Metals are malleable as the layers can slide over each and reform
Covalent bonding & simple covalent lattice structures
• Simple covalent lattices have low melting and boiling points
o These compounds have weak intermolecular forces between the molecules
o Only little energy is required to break the lattice
• Most compounds are insoluble with water
o Unless they are polar (such as HCl) or can form hydrogen bonds (such as NH3)
• They do not conduct electricity in the solid or liquid state as there are no charged
particles
o Some simple covalent compounds to conduct electricity in solution such as HCl
which forms H+ and Cl– ions
Covalent bonding & giant covalent lattice structures
• Giant covalent lattices have melting and boiling points
o These compounds have a large number of covalent bonds linking the whole
structure intermolecular forces between the molecules
o A lot of energy is required to break the lattice
• The compounds can be hard or soft
o Graphite is soft as the forces between the carbon layers are weak
o Diamond and silicon(IV) oxide are hard as it is difficult to break their 3D
network of strong covalent bonds
• Most compounds are insoluble with water
• Most compounds do not conduct electricity however some do
o Graphite has delocalised electrons between the carbon layers which can move
along the layers when a voltage is applied
o Diamond and silicon(IV) oxide do not conduct electricity as all four outer
electrons on every carbon atom is involved in a covalent bond so there are no
free electrons available
Characteristics of different compound structure types table
Worked example: Bonding & structure

Answer
The correct answer is 4
The relatively high melting point, solubility in water and electrical conductivity when molten
suggest that X is a giant ionic structure.
The low melting point of Y suggests that little energy is needed to break the lattice which
corresponds to a simple molecular structure. This is further supported by the low electrical
conductivity and its being almost insoluble in water.
Compound Z has a very high melting point which is characteristic of either metallic or giant
molecular lattices, however since it conducts electricity, compound Z must be a giant metallic
lattice.

Summary
• The kinetic theory of gases states that gas particles are always in constant random motion at a
variety of speeds.
• The volume of a gas increases when the temperature increases and decreases when the
pressure increases.
• The volume of a gas under different conditions of temperature and pressure can be calculated
using the ideal gas equation pV = nRT.
• The ideal gas equation can be used to determine the relative molecular mass of simple
molecules.
• Gases do not obey the ideal gas equation at low temperatures and high pressures.
• The kinetic-molecular model can be used to describe the states of matter in terms of proximity
and motion of the particles, and to describe changes of state and vapour pressure.
Continued
• Ionic compounds such as sodium chloride and magnesium oxide form a giant three-
dimensional lattice structure containing ions in a regularly repeating pattern.
• The strong ionic forces acting in all directions between the ions in the lattice cause ionic
substances to have high melting and boiling points.
• Simple molecular solids with low melting points such as iodine have a regular arrangement
of molecules; they are crystalline. There are weak intermolecular forces between the
molecules.
• Giant covalent (giant molecular) structures such as diamond have a large number of
covalent bonds arranged in a regularly repeating pattern.
• Fullerenes are allotropes of carbon in the shape of hollow spheres (buckminsterfullerene)
or tubes (nanotubes).
• Graphene is composed of a single flat sheet of hexagonally-arranged carbon atoms.
• The strong covalent bonds between the atoms in giant molecular structures cause these
substances to have high melting and boiling points.
• In metals, the atoms are closely packed in a giant lattice in which the outer electrons are
free to move.
• Metals such as aluminium and copper and their alloys have a variety of uses, which can be
related to their physical properties, e.g. density, malleability, conductivity, hardness.
• Physical data can be used to suggest the type of structure and bonding present in a
substance.
• Recycling plays an important part in conserving finite resources such as metals.
END OF CHAPTER QUESTION:

1. Four types of structure are:

giant molecular
giant ionic
giant metallic
simple molecular
a. Give two examples of a giant ionic structure and two examples of a simple molecular
structure. [4]
b. Explain why substances with giant ionic structures are often brittle but metallic
structures are malleable. [6]
c. Explain why giant molecular structures have higher melting points than simple
molecular structures. [6]
d. Diamond and graphite are two forms of carbon with giant molecular structures.
Explain why graphite conducts electricity but diamond does not. [5]
Total = 21
2. Calculate the volume occupied by 0.500 mol of carbon dioxide at a pressure of 150 kPa
and a temperature of 19 °C. (R = 8.31 J K–1 mol–1) Total = 4
3. A flask of volume 5.00 dm3 contained 4.00 g of oxygen. Calculate the pressure exerted
by the gas at a temperature of 127 °C. (R = 8.31 J K–1 mol–1; Mr oxygen = 32.0)
Total = 4
4. A flask of volume 2.0 dm3 was found to contain 5.28 g of a gas. The pressure in the flask
was 200 kPa and the temperature was 20 °C. Calculate the relative molecular mass of the
gas. (R = 8.31 J K–1 mol–1) Total = 4
CHAPTER 5
CHEMICAL ENERGETICS
Learning Objectives:
5.1 Enthalpy change, ΔH
5.2 Hess’s Law

Learning Outcomes:
Candidates should be able to:

→ Understand that chemical reactions are accompanied by enthalpy changes and these changes can
be exothermic (ΔH is negative) or endothermic (ΔH is positive)
→ Construct and interpret a reaction pathway diagram, in terms of the enthalpy change of the
reaction and of the activation energy
→ Define and use the terms:
(a) standard conditions (this syllabus assumes that these are 298 K and 101 kPa) shown by ⦵.
(b) enthalpy change with particular reference to: reaction, ΔHr , formation, ΔHf , combustion,
ΔHc , neutralisation, ΔHneut
→ Understand that energy transfers occur during chemical reactions because of the breaking and
making of chemical bonds
→ Use bond energies (ΔH positive, i.e. bond breaking) to calculate enthalpy change of reaction,
ΔHr
→ Understand that some bond energies are exact and some bond energies are averages
→ Calculate enthalpy changes from appropriate experimental results, including the use of the
relationships q = mcΔT and ΔH = –mcΔT
→ Apply Hess’s Law to construct simple energy cycles
→ Carry out calculations using cycles and relevant energy terms, including:
(a) determining enthalpy changes that cannot be found by direct experiment
(b) use of bond energy data
 INTRODUCTION:
When chemical reactions take place there is an energy change. Energy can take many
forms, including heat, light, sound and electrical energy. The chemical energy in the atoms and
bonds of a substance is also very important. One of the most obvious energy transfers in
chemical reactions is the transfer of heat. A car engine gets hot when the energy is transfer
from the burning fuel. Fireworks release a lot of energy as heat (as well as light and sound)
when they explode. Our bodies keep warm because of the continuous oxidation of the food we
eat.

The chemical reactions in this fire are releasing large quantities of energy.

5.1Enthalpy change, ΔH
Enthalpy Changes
• The total chemical energy inside a substance is called the enthalpy (or heat content)
• When chemical reactions take place, changes in chemical energy take place and therefore
the enthalpy changes
• An enthalpy change is represented by the symbol ΔH (Δ= change; H = enthalpy)
• An enthalpy change can be positive or negative
Exothermic reactions
• A reaction is exothermic when the products have less energy than the reactants
• Heat energy is given off by the reaction to the surroundings
o The temperature of the environment increases – this can be measured on a
thermometer
o The temperature of the system decreases
• There is an enthalpy decrease during the reaction so ΔH is negative
• Exothermic reactions are thermodynamically possible (because the enthalpy of the
reactants is higher than that of the products)
• However, if the rate is too slow, the reaction may not occur
o In this case the reaction is kinetically controlled
 The enthalpy change during an exothermic reaction
Endothermic reactions
• A reaction is endothermic when the products have more energy than the reactants
• Heat energy is absorbed by the reaction from the surroundings
o The temperature of the environment decreases – this can be measured with a
thermometer
o The temperature of the system increases
• There is an enthalpy increase during the reaction so ΔH is positive

The enthalpy change during an endothermic reaction

Exam Tip
It is important to specify the physical states of each species in an equation when dealing with
enthalpy changes as any changes in state can cause very large changes of enthalpy.
For example:
Na⁺Cl⁻ (s) → Na⁺ (aq) + Cl⁻ (aq) ΔH = +4 kJ mol⁻¹
Na⁺Cl⁻ (g) → Na⁺ (g) + Cl⁻ (g) ΔH = + 500 kJ mol⁻¹
Also, remember that the system is the molecules that are reacting (ie. the reaction itself) and the
surroundings is everything else (eg. the flask the reaction is taking place in).
Energy Level Diagrams
• An energy level diagram is a diagram that shows the energies of the reactants, the
transition state(s) and the products of the reaction with time
• The transition state is a stage during the reaction at which chemical bonds are partially
broken and formed
• The transition state is very unstable – it cannot be isolated and is higher in energy than
the reactants and products
• The activation energy (Ea) is the energy needed to reach the transition state
• We can define the activation energy as ‘the minimum amount of energy needed for
reactant molecules to have a successful collision and start the reaction’

The energy level diagram for the reaction of hydrogen with chlorine to form hydrogen
chloride gas
Exothermic reaction
• In an exothermic reaction, the reactants are higher in energy than the products
• The reactants are therefore closer in energy to the transition state
• This means that exothermic reactions have a lower activation energy compared to
endothermic reactions

The energy level diagram for exothermic reactions

Endothermic reaction
• In an endothermic reaction, the reactants are lower in energy than the products
• The reactants are therefore further away in energy to the transition state
• This means that endothermic reactions have a higher activation energy compared to
exothermic reactions

The energy level diagram for endothermic reactions

Worked example: Drawing energy level diagrams of the combustion of methane

Answer
• Step 1: The chemical equation for the complete combustion of methane is:
CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (l)
• Step 2: Combustion reactions are always exothermic (ΔH is negative) so the reactants
should be drawn higher in energy than the products
 • Step 3: Draw the curve in the energy level diagram clearly showing the transition state

• Step 4: Draw arrows to show the Ea and ΔH including their values

Worked example: Determining the activation energy

The reaction pathway diagram for a reversible reaction

Answer
The Ea is the energy difference from the energy level of the reactants to the top of the ‘hump’
Ea (forward reaction) = (+70 kJ mol-1) + (+ 20 kJ mol-1 ) = +90 kJ mol-1
As the question is asking for the reverse reaction the Ea is the energy difference from the
energy level of the products to the ‘hump’
Ea (reverse reaction) = +20 kJ mol-1

Exam Tip
The activation energy is the energy difference from reactants to transition state.
The enthalpy change of the reaction is the energy difference from reactants to products.
Remember to label the axis of the energy level diagrams!

Enthalpy Changes at Standard Conditions

• To fairly compare the changes in enthalpy between reactions, all reactions should be
carried out under standard conditions
• These standard conditions are:
o A pressure of 101 kPa
o A temperature of 298 K (25 oC)
o Each substance involved in the reaction is in its normal physical state (solid, gas
or liquid)
• To show that a reaction has been carried out under standard conditions, the symbol Ꝋ is
used
o ΔHꝊ = the standard enthalpy change
• These are a number of key definitions for common language relating to enthalpy change
that all chemists need to know
Enthalpy definitions table
Worked example: Calculating the enthalpy change of reaction of water

Answer
Since two moles of water molecules are formed in the question above, the energy released is
simply:
ΔHrꝊ = 2 mol x (-286 kJ mol-1)
= -572 kJ mol-1

Worked example: Calculating the enthalpy change of formation

Answer
Since two moles of Fe2O3 (s) are formed the total change in enthalpy for the reaction above is:
ΔHfꝊ = 2 x ( -824.2 kJ mol-1)
= – 1648 kJ

Worked example: Calculating enthalpy changes

Answer
Answer 1: ΔHrꝊ
Answer 2: ΔHrꝊ as one mole of CO2 is formed from its elements in standard state and ΔHcꝊ as
one mole of carbon is burnt in oxygen
Answer 3: ΔHneutꝊ as one mole of water is formed from the reaction of an acid and alkali

Exam Tip
The ΔHfꝊ of an element in its standard state is zero.
For example, ΔHfꝊ of O2(g) is 0 kJ mol-1

Enthalpy & Bond Energies

• During a reaction, enthalpy changes take place because bonds are being broken and
formed
• Energy (in the form of heat) is needed to overcome attractive forces between atoms
• Bond breaking is therefore endothermic
 • Energy is released from the reaction to the surroundings (in the form of heat) when new
bonds are formed
• Bond forming is therefore exothermic

To break bonds energy is required from the surroundings and to make new bonds energy is
released from the reaction to the surroundings
• If more energy is required to break bonds than energy is released when new bonds are
formed, the reaction is endothermic
• If more energy is released when new bonds are formed than energy is required to break
bonds, the reaction is exothermic
• In reality, only some bonds in the reactants are broken and then new ones are formed

Enthalpy Calculations
Exact bond energy
• The amount of energy required to break one mole of a specific covalent bond in the gas
phase is called the bond dissociation energy
• Bond dissociation energy (E) is also known as exact bond energy or bond enthalpy
• The type of bond broken is put in brackets after E
o Eg. EE(H-H) is the bond energy of a mole of single bonds between two hydrogen
atoms
Average bond energy
• Bond energies are affected by other atoms in the molecule (the environment)
• Therefore, an average of a number of the same type of bond but in different
environments is calculated
• This bond energy is known as the average bond energy
• Since bond energies cannot be determined directly, enthalpy cycles are used to calculate
the average bond energy
 Bond energies are affected by other atoms in the molecule

Calculating enthalpy change from bond energies

• Bond energies are used to find the ΔHrꝋ of a reaction when this cannot be done
experimentally
• Eg. the Haber Process

Formula of calculating the standard enthalpy change of reaction using bond energies

Worked example: Calculating the enthalpy change in the Haber process

Answer
• Step 1: The chemical equation for the Haber process is:
N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
• Step 2: Set out the calculation as a balance sheet as shown below:

Note! Values for bonds broken are positive (endothermic) and values for bonds formed are
negative (exothermic)
 • Step 3: Calculate the standard enthalpy of reaction
ꝋ
ΔHr = enthalpy change for bonds broken + enthalpy change for bonds formed
= (+2253 kJ mol-1) + (-2346 kJ mol-1)
= -93 kJ mol-1

Worked example: Calculating the average bond enthalpy

Answer
• Step 1: The enthalpy of combustion is the enthalpy change when one mole of a
substance reacts in excess oxygen to produce water and carbon dioxide
The chemical reaction should be therefore simplified such that only one mole of ethyne reacts in
excess oxygen:
H-C=C-H + 2 ½ O=O → H-O-H + 2O=C=O
• Step 2: Set out the calculation as a balance sheet as shown below:

ΔHrꝋ = enthalpy change for bonds broken + enthalpy change for bonds formed
= (+258 kJ mol-1) + (-418 kJ mol-1)
= -133 kJ mol-1
Measuring enthalpy changes
• Calorimetry is a technique used to measure changes in enthalpy of chemical reactions
• A calorimeter can be made up of a polystyrene drinking cup, a vacuum flask or metal
can

A polystyrene cup can act as a calorimeter to find enthalpy changes in a chemical reaction
• The energy needed to increase the temperature of 1 g of a substance by 1 oC is called the
specific heat capacity (c) of the liquid
• The specific heat capacity of water is 4.18 J g-1 oC-1
• The energy transferred as heat can be calculated by:

Equation for calculating energy transferred in a calorimeter

Worked example: Specific heat capacity calculations

• Step 1: q = m x c x ΔT
m (of water) = 500 g
c (of water) = 4.18 J g-1 K-1
ΔT (of water) = 68 oC – 25 oC
= 43 oC
= 43 K
The change in temperature in oC is equal to the change in temperature in K
 • Step 2: q = 500 x 4.18 x 43
= 89 870 J
• Step 3: This is only 30% of the total energy released by methane
Total energy x 0.3 = 89 870 J
Total energy = 299 567 J
• Step 4: This is released by 2.50 g of methane

= 119 827 J
= 120 kJ
Exam Tip
When new bonds are formed the amount of energy released is equal to the amount of energy
absorbed when the same bonds are broken.
For example:
O2 (g) → 2O (g) E (O=O) = +498 kJ mol-1
2O (g) → O2 (g) E (O=O) + -498 kJ mol-1

Aqueous solutions of acid, alkalis and salts are assumed to be largely water so you can just use
the m and c values of water when calculating the energy transferred. To then calculate any
changes in enthalpy per mole of a reactant or product the following relationship can be
used: When there is a rise in temperature, the value for ΔH becomes negative suggesting that the
reaction is exothermic and when the temperature falls, the value for ΔH becomes positive
suggesting that the reaction is endothermic.
Also, remember that the ΔT is the same in oC and K!

5.2Hess’s Law
Hess Cycles
• Hess’s Law states that:
“The total enthalpy change in a chemical reaction is independent of the route by
which the chemical reaction takes place as long as the initial and final conditions are
the same.”
• This means that whether the reaction takes place in one or two steps, the total enthalpy
change of the reaction will still be the same

The diagram above illustrates Hess’ Law: the enthalpy change of the direct route, going from
reactants (A+B) to product (C) is equal to the enthalpy change of the indirect routes
 • Hess’ Law is used to calculate enthalpy changes which can’t be found experimentally
using calorimetry, eg:
3C (s) + 4H2 (g) → C3H8(g)
• ΔHf (propane) can’t be found experimentally as hydrogen and carbon don’t react under
standard conditions
Calculating ΔHr from ΔHf using Hess’s Law energy cycles
• The products can be directly formed from the elements = ΔH2
OR
• The products can be indirectly formed from the elements = ΔH1 + ΔHr

The enthalpy change from elements to products (direct route) is equal to the enthalpy change
of elements forming reactants and then products (indirect route)

• Equation
ΔH2 = ΔH1 + ΔHr
Therefore,
ΔHr = ΔH2 – ΔH1
Worked example: Calculating the enthalpy change of reaction

• Step 1: Write the balanced equation at the top

• Step 2: Draw the cycle with the elements at the bottom

 • Step 3: Draw in all arrows, making sure they go in the correct directions. Write the
standard enthalpy of formations

• Step 4: Apply Hess’s Law

Calculating ΔHf from ΔHc using Hess’s Law energy cycles

• The combustion products can be formed directly from elements to combustion products =
ΔH1
OR
• The combustion products can be formed indirectly from elements to compound to
combustion products = ΔHf+ ΔH2

The enthalpy change going from elements to products (direct route) is equal to the enthalpy
change of elements forming reactants and then products (indirect route)
• Equation
ΔH1 = ΔHf + ΔH2
Therefore,
ΔHf = ΔH1 – ΔH2
Worked example: Calculating the enthalpy change of formation of ethane
 • Step 1: Write the equation for enthalpy change of formation at the top and add oxygen on
both sides

• Step 2: Draw the cycle with the combustion products at the bottom

• Step 3: Draw all arrows in the correct direction

• Step 4: Apply Hess’s Law

Calculating average bond energies using Hess’s cycles

• Bond energies cannot be found directly so enthalpy cycles are used to find the average
bond energy
• This can be done using enthalpy changes of atomisation and combustion or formation
• The enthalpy change of atomisation (ΔHatꝋ ) is the enthalpy change when one mole of
gaseous atoms is formed from its elements under standard conditions.
o Eg. ΔHatꝋ [H2] relates to the equation:
½ H2(g) → H(g)

Worked example: Calculating average C-H bond energy

 • Step 1: Write down the equation for the dissociation of methane at the top

• Step 2: Write down the elements at the bottom

• Step 3: Draw all arrows in the correct direction

• Step 4: Apply Hess’s Law

• Step 5: Since there are 4 C-H bonds in methane:

Exam Tip
Remember to take into account the number of moles of each reactant and product.
For example, there are two moles of NaHCO3(s) so the ΔHf value is multiplied by 2.

Summary
• When a chemical reaction occurs, energy is transferred to or from the surroundings.
• In an exothermic reaction, heat is given out to the surroundings so the products have less
energy than the reactants. In an endothermic reaction, heat is absorbed from the surroundings
so the products have more energy than the reactants.
• Energy changes in chemical reactions that lead to heating or cooling are called enthalpy
changes (ΔH).
• Exothermic enthalpy changes are shown as negative values (–).
• Endothermic enthalpy changes are shown as positive values (+).
• Standard enthalpy changes are compared under standard conditions of pressure, 105 Pa (100
kPa), and temperature, 298 K (25 °C).
• Enthalpy changes can be calculated experimentally using the relationship: enthalpy change =
–mass of liquid × specific heat capacity × temperature change ΔH = –mcΔT
Continued:
• The standard enthalpy change of formation is the enthalpy change when one
mole of a compound is formed from its elements under standard conditions.

• The standard enthalpy change of combustion is the enthalpy change when one
mole of a substance is burnt in excess oxygen under standard conditions.

• The standard enthalpy change of atomisation is the enthalpy change when one
mole of gaseous atoms is formed from the element in its standard state under standard
conditions.
• The standard enthalpy changes of hydration and solution can be defined in terms of one
mole of a specified compound reacting completely.
• The standard enthalpy change of neutralisation can be defined in terms of one mole of
water formed when hydrogen ions and hydroxide ions react.
• Hess’s law states that ‘the total enthalpy change for a chemical reaction is independent
of the route by which the reaction takes place’.
• Hess’s law can be used to calculate enthalpy changes for reactions that do not occur
directly or cannot be found by experiment.
• Hess’s law can be used to calculate the enthalpy change of a reaction using the enthalpy
changes of formation of the reactants and products.
• Hess’s law can be used to calculate the enthalpy change of formation of a compound
using the enthalpy changes of combustion of the reactants and products.
• Bond breaking is endothermic; bond making is exothermic.
• Bond energy is a measure of the energy needed to break a covalent bond.
• Average bond energies are often used because the strength of a bond between two
particular types of atom is slightly different in different compounds.
• Hess’s law can be used to calculate the enthalpy change of a reaction using the average
bond energies of the reactants and products.
CHAPTER 6
THE PERIODIC TABLE: CHEMICAL PERIODICITY

Learning Objectives:
6.1 Periodicity of physical properties of the elements in Period 3
6.2 Periodicity of chemical properties of the elements in Period 3
6.3 Chemical periodicity of other elements

Learning Outcomes:
Candidates should be able to:

→ Describe qualitatively (and indicate the periodicity in) the variations in atomic radius, ionic
radius, melting point and electrical conductivity of the elements
→ Explain the variation in melting point and electrical conductivity in terms of the structure and
bonding of the elements
→ Describe, and write equations for, the reactions of the elements with oxygen (to give Na₂O,
MgO, Al₂O₃, P₄O10, SO₂), chlorine (to give NaCl, MgCl₂, AlCl₃, SiCl₄, PCl₅) and water (Na and
Mg only)
→ State and explain the variation in the oxidation number of the oxides (Na₂O, MgO, Al₂O₃,
P₄O10, SO₂ and SO₃ only) and chlorides (NaCl, MgCl₂, AlCl₃, SiCl ₄, PCl₅ only) in terms of their
outer shell (valence shell) electrons
→ Describe, and write equations for, the reactions, if any, of the oxides Na₂O, MgO, Al₂O₃, SiO₂,
P₄O10, SO₂ and SO₃ with water including the likely pHs of the solutions obtained
→ Describe, explain, and write equations for, the acid / base behaviour of the oxides Na₂O, MgO,
Al₂O₃, P₄O10, SO₂ and SO₃ and the hydroxides NaOH, Mg(OH)₂, Al(OH) ₃ including, where
relevant, amphoteric behaviour in reactions with acids and bases (sodium hydroxide only)
→ Describe, explain, and write equations for, the reactions of the chlorides NaCl, MgCl₂, AlCl₃,
SiCl₄, PCl₅ with water including the likely pHs of the solutions obtained
→ Explain the variations and trends in 9.2.2, 9.2.3, 9.2.4 and 9.2.5 in terms of bonding and
electronegativity
→ Suggest the types of chemical bonding present in the chlorides and oxides from observations of
their chemical and physical properties
→ Predict the characteristic properties of an element in a given group by using knowledge of
chemical periodicity
→ Deduce the nature, possible position in the Periodic Table and identity of unknown elements
from given information about physical and chemical properties
 INTRODUCTION:
The Periodic Table was devised in 1869 by Russian chemist Dmitri Mendeleev. He
organised the elements known at that time in order of their atomic mass, arranging elements
with similar properties into vertical columns. He left gaps where the pattern broke down,
arguing that these spaces would eventually be filled by as-yet undiscovered elements. For
example, he left a space below silicon, and he made predictions of how the ‘new’ element
would behave when it was discovered. He also changed the atomic mass order in places where
similar elements did not quite line up in columns. These apparent inconsistencies resulted in
some of his fellow chemists doubting the relevance of his table, but they were convinced
following the discovery of germanium in 1886. Germanium closely matched the properties
that Mendeleev had predicted for the ‘new’ element below silicon, using his Periodic Table.

Figure a Dmitri Mendeleev (1834–1907). b This version of

Mendeleev’s Periodic Table is on the building in St Petersburg
where he worked.

6.1 Periodicity of physical properties of the elements in Period 3

Structure of the Periodic Table
We now know that the chemical elements are arranged in the Periodic Table in order of atomic number,
not atomic masses as first thought. This explains why Mendeleev had to re-order some elements in his
table (which was developed before scientists knew about the structure of the atom). There are 18 groups
(vertical columns) in the Periodic Table. The rows across the table are called periods. In this chapter we
will be looking for patterns going across the third period, from sodium (Na) to argon (Ar). The patterns
seen across Period 3 are seen across other periods, too. This recurrence of the same pattern is called
periodicity.

Properties of the Elements in Period 3

• Elements in the periodic table are arranged in order of increasing atomic number and
placed in vertical columns (groups) and horizontal rows (periods)
• The elements across the periods show repeating patterns in chemical and physical
properties
• This is called periodicity
 All elements are arranged in the order of increasing atomic number from left to right

Atomic radius
• The atomic radius is the distance between the nucleus and the outermost electron of an
atom
• The atomic radius is measured by taking two atoms of the same element, measuring the
distance between their nuclei and then halving this distance
• In metals this is also called the metallic radius and in non-metals, the covalent radius
 The atomic radius gives a measure of the size of atoms

Atomic radii of Period 3 elements table

The graph shows a decrease in atomic radii of Period 3 elements across the period
• Across the period, the atomic radii decrease
• This is because the number of protons (the nuclear charge) and the number of electrons
increases by one every time you go an element to the right
• The elements in a period all have the same number of shells (so the shielding effect is the
same)
• This means that as you go across the period the nucleus attracts the electrons more
strongly pulling them closer to the nucleus
• Because of this, the atomic radius (and thus the size of the atoms) decreases across the
period
 The diagram shows that across Period 3, the elements gain extra electrons in the same
principal quantum shell

Ionic radius
• The ionic radius is the distance between the nucleus and the outermost electron of an ion
• Metals produce positively charged ions (cations) whereas nonmetals produce negatively
charged ions (anions)
• The cations have lost their valence electrons which causes them to be much smaller than
their parent atoms
• Because there are less electrons, this also means that there is less shielding of the outer
electrons
• Going across the period from Na+ to Si4+ the ions get smaller due to the increasing
nuclear charge attracting the outer electrons in the second principal quantum shell
nucleus (which has an increasing atomic number)
• The anions are larger than their original parent atoms because each atom has gained one
or more electrons in their third principal quantum shell
• This increases the repulsion between electrons, while the nuclear charge is still the
same, causing the electron cloud to spread out
• Going across P3- to Cl– the ionic radii decreases as the nuclear charge increases across
the period and less electrons are gained by the atoms (P gains 3 electrons, S 2 electrons
and Cl 1 electron)

Ionic radii of ions of Period 3 elements table

 Ions of Period 3 elements with increasing positive charge (metals) and increasing of outer
electrons across the period

The diagram shows the electron configuration of the ions of Period 3 elements and their
relative sizes

Melting point
Melting points of the elements across Period 3 table
 Ions of Period 3 elements with increasing positive charge (metals) and increasing of outer
electrons across the period
• A general increase in melting point for the Period 3 elements up to silicon is observed
• Silicon has the highest melting point
• After the Si element the melting points of the elements decreases significantly
Electrical conductivity
• Electrical conductivity refers to how well a substance can conduct electricity
• Unlike the melting points, the electrical conductivity of the Period 3 elements shows a
clear trend
• Going across the period, the electrical conductivity of the elements decreases
significantly
Trends in electrical conductivity across Period 3 table

Period 3: Structure & Bonding

Melting point
Melting points of the elements across Period 3 table
 Ions of Period 3 elements with increasing positive charge (metals) and increasing of outer
electrons across the period
• The above trends can be explained by looking at the bonding and structure of the
elements

Bonding & structure of the elements table

• The table shows that Na, Mg and Al are metallic elements which form positive ions
arranged in a giant lattice in which the ions are held together by a ‘sea’ of delocalised
electrons around them

Metal cations form a giant lattice held together by electrons that can freely move around
 • The electrons in the ‘sea’ of delocalised electrons are those from the valence shell of the
atoms
• Na will donate one electron into the ‘sea’ of delocalised electrons, Mg will donate two
and Al three electrons
• As a result of this, the metallic bonding in Al is stronger than in Na
• This is because the electrostatic forces between a 3+ ion and the larger number of
negatively charged delocalised electrons is much larger compared to a 1+ ion and the
smaller number of delocalised electrons in Na
• Because of this, the melting points increase going from Na to Al
• Si has the highest melting point due to its giant molecular structure in which each Si atom
is held to its neighbouring Si atoms by strong covalent bonds
• P, S, Cl and Ar are non-metallic elements and exist as simple molecules (P4, S8, Cl2 and
Ar as a single atom)
• The covalent bonds within the molecules are strong, however, between the molecules,
there are only weak instantaneous dipole-induced dipole forces
• It doesn’t take much energy to break these intermolecular forces
• Therefore, the melting points decrease going from P to Ar (note that the melting point of
S is higher than that of P as sulphur exists as larger S8 molecules compared to the smaller
P4 molecule)

Electrical conductivity
• The electrical conductivity decreases going across the Period 3 elements
Electrical conductivity decreases Period 3 elements table

• Going from Na to Al, there is an increase in the number of valence electrons that are
donated to the ‘sea’ of delocalised electrons
• Because of this, in Al there are more electrons available to move around through the
structure when it conducts electricity, making Al a better electrical conductor than Na
• Due to the giant molecular structure of Si, there are no delocalised electrons that can
freely move around within the structure
• Si is therefore not a good electrical conductor and is classified as a semimetal
(metalloid)
• The lack of delocalised electrons is also why P and S cannot conduct electricity
Period 3: Oxides
Reactions with oxygen & chlorine
Reaction of Period 3 elements with oxygen table

Reaction of Period 3 elements with chlorine table

Reaction of sodium & magnesium with water

• Sodium reacts vigorously with cold water:
2Na(s) + 2H2O(l) → 2NaOH(aq) + H2(g)
• The sodium melts into a ball and moves across the water surface until it disappears
• Hydrogen gas is given off
• The solution formed is strongly alkaline (pH 14) due to the sodium hydroxide which is
formed
 The diagram shows the reaction of sodium with cold water
• Magnesium reacts extremely slowly with cold water:
Mg(s) + 2H2O(l) → Mg(OH)2(aq) + H2(g)
• The solution formed is weakly alkaline (pH 11) as the formed magnesium hydroxide is
only slightly soluble
• When magnesium is heated, it reacts vigorously with steam (water) to make magnesium
oxide and hydrogen gas:
Mg(s) + H2O(g) → MgO(s) + H2(g)

Oxidation Number of the Period 3 Oxides

• Oxygen is more electronegative than any of the Period 3 elements

The Pauling scale shows the electronegativities of the elements in the periodic table. Oxygen
has a higher electronegativity than any of the Period 3 elements which is why the Period 3
elements will have positive oxidation states and the oxygen a negative oxidation state in the
oxides of Period 3 elements
• The Period 3 elements therefore have positive oxidation states in their oxides and the
oxygen has a negative oxidation state of -2
Oxidation states of the Period 3 elements in their oxides
Formulae of the oxides of the Period 3 elements & their oxidation states table

Reaction of Period 3 Oxides & Water

• Not all Period 3 oxides react with or are soluble in water
Reaction of Period 3 oxides with water table
6.2 Periodicity of chemical properties of the elements in Period 3
Acid / Base Behaviour of Period 3 Oxides & Hydroxides
Period 3 oxides
• Aluminium oxide is amphoteric which means that it can act both as a base (and react
with an acid such as HCl) and an acid (and react with a base such as NaOH)

Acidic & basic nature of the Period 3 oxides

Reactions of the Period 3 oxides with acid/base table

• The acidic and basic nature of the Period 3 elements can be explained by looking at their
structure, bonding and the Period 3 elements’ electronegativity
Structure, bonding & electronegativity of the Period 3 elements table

• The difference in electronegativity between oxygen and Na, Mg and Al is the largest
• Electrons will therefore be transferred to oxygen when forming oxides giving the oxide
an ionic binding
• The oxides of Si, P and S will share the electrons with the oxygen to form covalently
bonded oxides
• The giant ionic and giant covalent structured oxides will have high melting points as it
is difficult to break the structures apart

The diagram shows the structure of some Period 3 oxides

 • The oxides of Na and Mg which show purely ionic bonding produce alkaline solutions
with water as their oxide ions (O2-) become hydroxide ions (OH–):
O2-(aq) + H2O(l) → 2OH–(aq)
• The oxides of P and S which show purely covalent bonding produce acidic solutions
with water because when these oxides react with water, they form an acid which donates
H+ ions to water
o Eg. SO3 reacts with water as follows:
SO3(g) + H2O(l) → H2SO4(aq)
•
o The H2SO4 is an acid which will donate a H+ to water:
H2SO4(aq) + H2O(l) → H3O+ (aq) + HSO4–(aq)
• Al and Si are insoluble and when they react with hot, concentrated alkaline solution
they act as a base and form a salt
o This behaviour is very typical of a covalently bonded oxide
• Al can also react with acidic solutions to form a salt and water
o This behaviour is very typical of an ionic bonded metal oxide
• This behaviour of Al proves that the chemical bonding in aluminium oxide is not purely
ionic nor covalent: it is amphoteric

Period 3 hydroxide
• NaOH is a strong base and will react with acids to form a salt and water:
NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l)
• Mg(OH)2 is also a basic compound which is often used in indigestion remedies by
neutralising the excess acid in the stomach to relieve pain:
Mg(OH)2(s) + 2HCl(aq) → MgCl2(aq) + 2H2O(l)
• Al(OH)3 is amphoteric and can acts both as an acid and base:
Al(OH)3(s) + 3HCl(aq) → AlCl3(s) + 3H2O(l)
Al(OH)3(s) + NaOH(aq) → NaAl(OH)4(aq)
Exam Tip
Electronegativity is the power of an element to draw the electrons towards itself in a covalent
bond.
For example, in Na2O the oxygen will draw the electrons more strongly towards itself than
sodium does.
Reaction of Period 3 Chlorides & Water
• Chlorides of Period 3 elements show characteristic behaviour when added to water which
can be explained by looking at their chemical bonding and structure
Chemical bonding & structure of Period 3 chlorides table

Sodium & magnesium chloride

• NaCl and MgCl2 do not react with water as the polar water molecules are attracted to the
ions dissolving the chlorides and breaking down the giant ionic structures: the metal
and chloride ions become hydrated ions

The diagram shows water molecules breaking down the giant ionic structure of NaCl and
MgCl2 to form hydrated ions
Aluminium chloride
• Aluminium chloride exists in two forms:
o AlCl3 as a giant lattice and with ionic bonds
o Al2Cl6 as a dimer with covalent bonds
 The two forms in which aluminium chloride exists

• When water is added to aluminium chloride the dimers are broken down and Al3+ and Cl–
ions enter the solution
• The highly charged Al3+ ion becomes hydrated and causes a water molecule that is
bonded to the Al3+ to lose an H+ ion which turns the solution acidic
• The H+ and the Cl– form hydrogen chloride gas which is given off as white fumes

The hydrated aluminium causes a water molecule to lose a H+ ion turning the solution acidic
Silicon chloride
• SiCl4 is hydrolysed in water, releasing white fumes of hydrogen chloride gas in a
rapid reaction
SiCl4(l) + 2H2O(l) → SiO2(s) + 4HCl(g)
• The SiO2 is seen as a white precipitate and some of the hydrogen chloride gas
produced dissolves in water to form an acidic solution
Phosphorus(V) chloride
• PCl5 also gets hydrolysed in water
PCl5(s) + 4H2O(l) → H3PO4(aq) + 5HCl(g)
• Both H3PO4 and dissolved HCl are highly acidic
Period 3: Trends in Electronegativity & Bonding
Electronegativity
• Electronegativity is the power of an element to draw the electrons towards itself in a
covalent bond
• Going across the period, the electronegativity of the elements increases
Electronegativity across Period 3 table

The diagram shows the trends in electronegativity of the Period 3 elements

• As the atomic number increases going across the period, there is an increase in nuclear
charge
• Across the period, there is an increase in the number of valence shells however the
shielding is still the same as each extra electrons enters the same shell
• As a result of this, electrons will be more strongly attracted to the nucleus causing an
increase in electronegativity across the period
Bonding & structure of Period 3 elements

• The table shows that going from Al to S the bonding changes from metallic to covalent
and the structure changes from giant to simple structure
 • Na, Mg and Al are metallic elements which form positive ions arranged in a giant lattice
in which the ions are held together by a ‘sea’ of delocalised electrons around them
• Since Al donates three electrons into the sea of delocalised electrons to form an ion with
+3 charge, the electrostatic forces between the electrons and the aluminium ion will be
very strong
• The electrons in the ‘sea’ of delocalised electrons are those from the valence shell of the
atoms
• Na will donate one electron into the ‘sea’ of delocalised electrons, Mg will donate two
and Al three electrons
• As a result of this, the metallic bonding in Al is stronger than in Na
• This is because the electrostatic forces between a 3+ ion and the larger number of
negatively charged delocalised electrons are much larger compared to a 1+ ion and the
smaller number of delocalised electrons in Na
• Since there are more electrons in a metallic lattice of aluminium compared to sodium and
magnesium, aluminium is a better electrical conductor

Metal cations form a giant lattice held together by electrons that can freely move around
• Si is a non-metallic element and has a giant molecular structure in which each Si atom is
held to its neighbouring Si atoms by strong covalent bonds
• There are no delocalised electrons in the structure of Si which is why silicon cannot
conduct electricity and is classified as a metalloid

The diagram shows the giant molecular structure of silicon where silicon atoms are held
together by strong covalent bonds
 • Phosphorus, sulfur, chlorine argon re both non-metallic elements that exist as simple
molecules (P4 , S8 , Cl2 and Ar as single atoms)
• The covalent bonds within the molecules are strong, however, between the molecules
there are only weak instantaneous dipole-induced dipole forces
• It doesn’t take much energy to break these intermolecular forces
• The lack of delocalised electrons means that these compounds cannot conduct electricity

The diagram shows the simple molecular structure of phosphorus with covalent bonds
between the atoms

The diagram shows the simple molecular structure of sulfur with covalent bonds between the
atoms

Bonding in Period 3 Chlorides & Oxides

Period 3 chlorides
• The bonding and structure of the Period 3 elements are summarised in the table below:
• The table shows that Na, Mg and Al are metallic elements which form positive ions
arranged in a giant lattice in which the ions are held together by a ‘sea’ of delocalised
electrons around them
• The electrons in the ‘sea’ of delocalised electrons are those from the valence shell of the
atoms
• Na will donate one electron into the ‘sea’ of delocalised electrons, Mg will donate two
and Al three electrons
• As a result of this, the metallic bonding in Al is stronger than in Na
• This is because the electrostatic forces between a 3+ ion and the larger number of
negatively charged delocalised electrons is much larger compared to a 1+ ion and the
smaller number of delocalised electrons in Na
• Because of this, the melting points increase going from Na to Al
• Si has the highest melting point due to its giant molecular structure in which each Si atom
is held to its neighbouring Si atoms by strong covalent bonds
• P, S, Cl and Ar are non-metallic elements and exist as simple molecules (P4, S8, Cl2 and
Ar as single atom)
• The covalent bonds within the molecules are strong, however between the molecules
there are only weak instantaneous dipole-induced dipole forces
• It doesn’t take much energy to break these intermolecular forces
• Therefore, the melting points decrease going from P to Ar (note that the melting point of
S is higher than that of P as sulphur exists as larger S8 molecules compared to the smaller
P4 molecule)
• The presence of a ‘sea’ of delocalised electrons also determines whether the element is a
good conductor or not
• Going across the period the electrical conductivity of the elements decreases due to lack
of delocalised electrons
• The electronegativities of the Period 3 elements therefore determines the chemical
bonding and structure of their chlorides and oxides

• Going across Period 3, their chlorides and oxidised become more covalent and their
structure shifts from a giant ionic to a simple molecular structure
• Their reactions with water become more vigorous as a result of this as it becomes easier
to hydrolyse the chlorides and oxides
6.3 Chemical periodicity of other elements
Periodicity: Predicting Position & Properties
• If the chemical and physical properties of an element are known, the position of that
element in the Periodic Table can be predicted
• Similarly, predictions can be made about the physical and chemical properties of
elements if the position of the element in the Periodic Table is known

The diagram shows a flowchart of how to use the position and/or properties of an element to
make predictions about its behaviour

Worked example: Deducing the position of an element in the Periodic Table

Answer
Break the question down and systematically approach the question
• Step 1: ‘Element X forms a chloride, which reacts with water to form a solution of pH 1’
The low pH of the solution formed suggests that the chloride is a non-metallic chloride
(group 13 to 17)
• Step 2: ‘The oxide does not dissolve in or react with aqueous sodium hydroxide’
Since aluminium oxide does reaction with sodium hydroxide, element G cannot be Group
13
• Step 3: It forms an oxide which has a melting point of 1610 °C’
This suggests a giant molecular (covalent) structure which corresponds to Group 14
• Step 4: Element X cannot be carbon (which is in Group 14) as carbon dioxide is a gas
whereas the element X oxide is a solid (with a melting point of 1610 °C)
• Step 5: Element X is therefore a Group 14 element in Period 3 or lower
• Note that this is an example of predicting the position of an element based on its physical
and chemical properties
Worked example: Predicting physical and chemical properties of selenium

Answer
• Step 1: Selenium is a nonmetal in Group 16 and if compared to sulfur, its structure is
predicted to be a simple molecular structure
• Step 2: Physical properties of simple molecular structures are low melting points, do
not conduct electricity and are insoluble in water
• Step 3: Chemical properties are:
o Reaction with water: simple molecules do not react with water
o Reaction with oxygen: reacts with oxygen to form an oxide of SeO2 (if compared
with sulfur)
o Reaction with chlorine: reacts with chlorine to form simple molecule of SeCl2
which can react with the water vapour in air to form hydrogen chloride (if
compared with sulfur)
• Note that this is an example of predicting the chemical and physical properties of an
element based on its position in the Periodic Table
Worked example: Determining an unknown chloride compound

Answer
Answer 1:
Group 1 and 2 chlorides react with water to form colourless solutions of pH 6.5-7
Group 15 chlorides on the other hand react with water to form strong acidic solutions
Element X therefore belongs to Group 15 of the Periodic Table
Answer 2:
Group 15 chlorides gets hydrolysed in water, therefore this is a hydrolysis reaction
Answer 3:
The white fumes that are given off during this reaction is hydrogen chloride gas
Summary
• Periods in the Periodic Table are rows of elements whose outermost electrons are in the
same principal quantum shell.
• The atoms of neighbouring members differ by one proton and one electron (and usually
by one or more neutrons).
• Periodic variations may be observed across periods in physical properties such as
ionisation
• energies, atomic radii, ionic radii, melting points and electrical conductivities.
• The main influences on ionisation energies, atomic radii and ionic radii are:
– the size of the positive nuclear charge
– the distance of the outermost (valence) electrons from the nucleus
– the shielding effect on outer electrons by electrons in filled inner shells.
• In general, ionisation energies tend to increase across a period.
• Atomic radii decrease across a period due to increasing nuclear charge.
• Positive ions are much smaller than their atoms. Negative ions are slightly larger than
their atoms.
• Across a period, the structures of the elements change from giant metallic, through giant
molecular to simple molecular. Group 18 elements consist of individual atoms.
• Across a period, the oxides of Period 3 elements change from basic compounds with
ionic bonding through to giant molecular in the centre of the period (Group 14) with
silicon, going on to acidic covalently bonded simple molecules of the non-metal oxides.
Aluminium oxide (in Group 13) is amphoteric, exhibiting both basic and acidic
behaviour.
• Across a period, the chlorides of Period 3 elements change from ionic compounds that
dissolve in water to covalent compounds that are hydrolysed by water, releasing fumes of
hydrogen chloride and leaving an acidic solution.
CHAPTER 7
GROUP 2
Learning Objectives:
7.1 Similarities and trends in the properties of the Group 2 metals, magnesium to barium,
and their compounds

Learning Outcomes:
Candidates should be able to:

→ Describe, and write equations for, the reactions of the elements with oxygen, water and dilute
hydrochloric and sulfuric acids
→ Describe, and write equations for, the reactions of the oxides, hydroxides and carbonates with
water and dilute hydrochloric and sulfuric acids
→ Describe, and write equations for, the thermal decomposition of the nitrates and carbonates, to
include the trend in thermal stabilities
→ Describe, and make predictions from, the trends in physical and chemical properties of the
elements involved in the reactions in 10.1.1 and the compounds involved in 10.1.2, 10.1.3 and
10.1.5
→ State the variation in the solubilities of the hydroxides and sulfates

INTRODUCTION:
Elements from Group 2 are used in a wide range of applications. For example, Group 2 metals
produce coloured flames when heated, leading to their use in flares and fireworks. Magnesium
is used in powdered form in flares. The large surface area in a fine powder increases the rate of
reaction with oxygen. In military aircraft the heat given off from decoy magnesium flares
confuses the infrared detection systems in missiles so enemy fire cannot focus in and target the
aircraft

.
A military plane releasing its decoy flares to protect it from missile attack.
7.1 Similarities and trends in the properties of the Group 2 metals,
magnesium to barium, and their compounds
Physical Properties of Group 2 Elements
The elements in Group 2 of the Periodic Table are sometimes referred to as the alkaline earth
metals. As they are in Group 2, the elements have atoms whose electronic configurations end with two
electrons in their outermost principal quantum shell. These two outer electrons occupy an s subshell. Here
are the electronic configurations of the first five elements in Group 2:
Beryllium (Be) 1s²2s²
Magnesium (Mg) 1s²2s²2p⁶3s²
Calcium (Ca) 1s²2s²2p⁶3s²3p⁶4s²
Strontium (Sr) 1s²2s²2p⁶3s²3p⁶3d¹⁰04s²4p⁶5s²
Barium (Ba) 1s²2s²2p⁶3s²3p⁶3d¹⁰4s²4p⁶4d¹⁰5s²5p⁶6s²
One way of describing the size of an atom is its metallic radius. The metallic radius is half the distance
between the nuclei in a giant metallic lattice.

The metallic radius gives us a measure of the size of the atoms of metallic elements.

The atoms of Group 2 elements get larger going down the group as the outer two electrons
occupy a new principal quantum shell further from the nucleus.

The metallic radii of the Group 2 elements.

There are also general trends in other physical properties, such as melting point and density,
shown in table below:

The melting points and densities of the Group 2 elements.

Reactions of Group 2 Elements
• The Group 2 elements react with oxygen, water and dilute acids

Group 2 reactions table

Group 2 reactions with oxygen & water chemical equations

Group 2 reactions with dilute hydrochloric acid & dilute sulfuric acid chemical equations

• The reaction of all metals with oxygen follows the following general equation:
2M(s) + O2(g) → 2MO(s)
Where M is any metal in Group 2
Remember than Sr and Ba also form MO2
• The reaction of all metals with water follows the following general equation:
M(s) + 2H2O(l) → M(OH)2(s) + H2(g)
Except for, Be which does not react with water
• The reaction of all metals with dilute HCl follows the following general equation:
M(s) + 2HCl(aq) → MCl2(aq) + H2(g)
• The reaction of all metals with dilute H2SO4 follows the following general equation:
M(s) + H2SO4(aq) → MSO4(aq) + H2(g)
Remember that SrSO4 and BaSO4 are insoluble

Reactions of Group 2 Oxides, Hydroxides & Carbonates

Reactions of Group 2 oxides with water

• All Group 2 oxides are basic, except for BeO which is amphoteric (it can act both as an
acid and base)
• Group 2 oxides react water to form alkaline solutions which get more alkaline going
down the group
Group 2 oxide reactions with water table
 • Remember that:
oxide + water → hydroxide
And that calcium hydroxide is also called limewater

Reactions of Group 2 metals with acid

• The Group 2 metals will react with dilute acids to form colourless solutions of metal
salts
o For example, they will form colourless solutions of metal chlorides if reacted with
hydrochloric acid
• When metals react with an acid, the by-product of this reaction is hydrogen gas
Group 2 metal element reactions with dilute acids table

• When some of Group 2 metals react with sulfuric acid rather than hydrochloric, an
insoluble sulfate forms
• Going down the group, the Group 2 sulfates become less and less soluble
o Calcium sulfate is sparingly soluble, but strontium sulfate and barium sulfate are
insoluble
Reactions of Group 2 oxides with acid

• Group 2 sulfates also form when a Group 2 oxide is reacted with an acid
• The insoluble sulfates form at the surface of the oxide, which means that the solid oxide
beneath it can’t react with the acid
• This can be prevented to an extent by using the oxide in powder form and stirring, in
which case neutralisation can take place
• Remember that:
oxide + dilute hydrochloric acid → salt + water
oxide + dilute sulfuric acid → sulfate + water

Reactions of group 2 hydroxides

• The Group 2 metal hydroxides form colourless solutions of metal chlorides when they
react with a dilute acid
• The sulfates decrease in solubility going down the group (barium sulfate is an insoluble
white precipitate)

Group 2 hydroxide reactions with dilute acids table

• Remember that:
hydroxide + dilute acid → salt + water
hydroxide + dilute sulfuric acid → sulfate + water

Reactions of group 2 carbonates

• All Group 2 carbonates (except for BeCO3) are insoluble in water

• All Group 2 carbonates will form soluble chloride salts, water and carbon dioxide gas
when reacted with dilute hydrochloric acid
• The carbonates of Ca, Sr and Ba form as an insoluble sulfate layer on their solid
carbonates which stops any further reaction after the initial bubbling (effervescence) of
carbon dioxide gas is seen
Group 2 carbonate reactions with dilute acids
 • Remember that:
carbonate + dilute hydrochloric acid → salt + water + carbon dioxide
carbonate + dilute sulfuric acid → sulfate + water + carbon dioxide

Group 2: Thermal Decomposition of Nitrates & Carbonates

• Thermal decomposition is the breakdown of a compound into two or more different
substances using heat

Thermal decomposition of carbonates

• The Group 2 carbonates break down (decompose) when they are heated to form the
metal oxide and give off carbon dioxide gas
• The general equation for the decomposition of Group 2 carbonates is:

The thermal decomposition of magnesium carbonate to form magnesium oxide and carbon
dioxide gas
• Going down the group, more heat is needed to break down the carbonates

Thermal decomposition of nitrates

• The Group 2 nitrates break decomposed when they are heated to form the metal oxide,
oxygen gas and nitrogen dioxide gas (which is a brown toxic gas)
• Since the formed nitrogen dioxide gas is toxic, the decomposition of nitrates is often
carried out in a fume cupboard
 The diagram shows the thermal decomposition of magnesium nitrate to form magnesium
oxide, oxygen gas and nitrogen dioxide gas
• The general equation for the decomposition of Group 2 nitrates is:

• Going down the group, more heat is needed to break down the nitrates
o The smaller positive ions at the top of Group II will polarise the nitrate ions more
than the larger ions at the bottom of the group
o The more polarised they are, the more likely they are to thermally decompose

Group 2: Physical & Chemical Trends

Chemical trends

• All elements in Group 2 (also called alkali earth metals) have the two electrons in their
outermost principal quantum shell
• All Group 2 metals can form ionic compounds in which they donate these two
outermost electrons (so they act as reducing agents) to become an ion with +2 charge
(so they themselves become oxidised)
• Going down the group, the metals become more reactive
• This can be explained by looking at the Group 2 ionisation energies:
 The graph shows that both the first and second ionization energies decrease going down the
table
• The first ionisation energy is the energy needed to remove the first outer electron of an
atom
• The second ionisation energy is the energy needed to remove the second outer electron
of an atom
• The graph above shows that going down the group, it becomes easier to remove the outer
two electrons of the metals
• Though the nuclear charge on the nucleus increases going down the group (because
there are more protons), factors such as an increased shielding effect and a larger
distance between the outermost electrons and nucleus outweigh the attraction of the
higher nuclear charge
• As a result of this, the elements become more reactive going down the group as it gets
easier for the atoms to lose two electrons and become 2+ ions
• This trend is shown by looking at reactions of the Group 2 metals:
o With dilute hydrochloric acid: bubbles of hydrogen gas are given off much faster
indicating that the reactions become more vigorous
o With oxygen hydrochloric acid: the metals get more reactive with oxygen down
the group (Ba is so reactive, that it must be stored in oil to prevent it from reacting
with oxygen in air)

Physical trends

• Going down the group, the elements become larger as the outer two electrons occupy a
new principal quantum shell which is further away from the nucleus
The atomic radius of the Group 2 elements increases going down the group due to the addition
of an extra principal quantum shell

The graph shows a decrease in atomic radius going down the group
• The melting point of the elements decreases going down the group as the outer electrons
get further away from the nucleus
• This means that the attraction between the nucleus and the bonding electrons decreases
causing a decrease in melting point
 The graph shows a decrease in melting point going down the group
• As you go down the group, the density of the alkali earth metals increases

The graph shows an increase in density going down the group

Worked example: Predicting properties of radium

Answer
Property 1:
Since, Ra is in Group 2, it will form an ion with +2 charge to give Ra2+
Property 2:
The Group 2 oxides and hydroxides have general formula XO and X(OH)2 respectively where X
is the Group 2 element.
Therefore, radium oxide is RaO and radium hydroxide is Ra(OH)2
Property 3:
Radium is below barium so its atomic radius is larger than the atomic radius of barium.
This means that radium’s outermost electrons are even further away and are therefore even more
easily removed than barium’s outermost electron pair.
The first ionization energy is between 450-480 kJ mol-1
Property 4:
Radium’s outermost electrons are even further away than in barium and are therefore more easily
removed making radium more reactive than barium.
Property 5:
The Group 2 hydroxides become more soluble going down the group.
Radium hydroxide will therefore be more soluble than calcium hydroxide.
Property 6:
The Group 2 sulfates become less soluble going down the group.
Radium sulfate will therefore be less soluble than strontium sulfate.
Property 7:
The general equation for the reaction of Group 2 oxides with dilute hydrochloric acid is:
XO(s) + 2HCl(aq) → XCl2(aq) + H2O(l)
where X is the Group 2 element
The reaction of radium oxide with dilute hydrochloric acid is therefore:
RaO(s) + 2HCl(aq) → RaCl2(aq) + H2O(l)
Property 8:
Radium sulfate will be formed in this reaction, however the solubility of Group 2 sulfates
decreases going down the group, therefore a white precipitate of radium sulfate will be formed in
this reaction
Trends in Solubility in Group 2 Hydroxides & Sulfates

Group 2 hydroxides

• Going down the group, the solutions formed from the reaction of Group 2 oxides with
water become more alkaline
• When the oxides are dissolved in water, the following ionic reaction takes place:
O2- (aq) + H2O(l) → 2OH– (aq)
• The higher the concentration of OH– ions formed, the more alkaline the solution
• The alkalinity of the formed solution can therefore be explained by the solubility of the
Group 2 hydroxides
Solubility of the Group 2 hydroxides table

• The hydroxides dissolve in water as follows:

X(OH)2 (aq) → X(aq) + 2OH– (aq)
Where X is the Group 2 element
• When the metal oxides react with water, a Group 2 hydroxide is formed
• Going down the group, the solubility of these hydroxides increases
• This means that the concentration of OH– ions increases, increasing the pH of the
solution
• As a result, going down the group, the alkalinity of the solution formed increases when
Group 2 oxides react with water
 Going down the group, the solubility of the hydroxides increases which means that the
solutions formed from the reactions of the Group 2 metal oxides and water become more
alkaline going down the group

Group 2 sulfates

• The solubility of the Group 2 sulfates decreasing going down the group

Going down the group, the solubility of the sulfates decreases

Summary
• The Group 2 elements magnesium to barium are typical metals with high melting points
and they are good conductors of heat and electricity.
• Progressing down Group 2 from magnesium to barium, the atomic radius increases. This is
due to the addition of an extra shell of electrons for each element as the group is descended.
• The Group 2 elements magnesium to barium react with water to produce hydrogen gas and
the metal hydroxide, which may be only slightly soluble.
• The Group 2 elements magnesium to barium burn in air to form white solid oxides. These
oxides form hydroxides with water. The hydroxides get more soluble in water going down
the group so their solutions can become more alkaline.
• The sulfates of Group 2 elements get less soluble in water going down the group.
• Reactivity of the elements with oxygen or water increases down Group 2 as the first and
CHAPTER 8
GROUP 17
Learning Objectives:
8.1 Physical properties of the Group 17 elements
8.2 The chemical properties of the halogen elements and the hydrogen halides
8.3 Some reactions of the halide ions
8.4 The reactions of chlorine

Learning Outcomes:
Candidates should be able to:

→ Describe the colours and the trend in volatility of chlorine, bromine and iodine
→ Describe and explain the trend in the bond strength of the halogen molecules
→ Interpret the volatility of the elements in terms of instantaneous dipole–induced dipole forces
→ Describe the relative reactivity of the elements as oxidising agents
→ Describe the reactions of the elements with hydrogen and explain their relative reactivity in these
reactions
→ Describe the relative thermal stabilities of the hydrogen halides and explain these in terms of
bond strengths
→ Describe the relative reactivity of halide ions as reducing agents
→ Describe and explain the reactions of halide ions with:
(a) aqueous silver ions followed by aqueous ammonia (the formation and formula of the
[Ag(NH₃)₂]⁺ complex is not required)
(b) concentrated sulfuric acid, to include balanced chemical equations
→ Describe and interpret, in terms of changes in oxidation number, the reaction of chlorine with
cold and with hot aqueous sodium hydroxide and recognise these as disproportionation
reactions
→ Explain, including by use of an equation, the use of chlorine in water purification to include the
production of the active species HOCl and ClO which kill bacteria.
 INTRODUCTION:
Fluorine, found at the top of Group 17, is the most reactive of all the non-metallic elements and
is a powerful oxidising agent. The next element in Group 17 is chlorine, also a toxic gas, but its
compounds, such as trichlorophenol, are important disinfectants. Compounds of carbon, fluorine
and chlorine are known as CFCs and have been responsible for most ofthe damage to the Earth’s
ozone layer.

Chlorine may be added to drinking water to kill harmful microorganisms.

8.1 Physical Properties of the Group 17 Elements

The elements in Group 17 of the Periodic Table, called the halogens. Their atoms all have seven
electrons in the outer principal quantum shell. Here are the electronic configurations of the first
four elements in Group 17:
Fluorine (F) 1s²2s²2p⁵
Chlorine (Cl) 1s²2s²2p6⁶3s²3p⁵
Bromine (Br) 1s²2s²2p⁶3s²3p⁶3d¹⁰4s²4p⁵
Iodine (I) 1s²2s²2p⁶3s²3p⁶3d¹⁰4s²4p⁶4d¹⁰5s²5p⁵
The Group 17 elements are all non-metals. At room temperature, they exist as diatomic
molecules, i.e. molecules made up of two atoms, F₂, Cl₂, Br₂ and I₂. There is a single covalent
bond between the two atoms in each molecule.

Some physical properties of the Group 17 elements. The atomic radius value is taken from
single covalent data
Group 17: Physical Trends
• The group 17 elements are called halogens
• The halogens have uses in water purification and as bleaches agents (chlorine), as flame-
retardants and fire extinguishers (bromine) and as antiseptic and disinfectant agents
(iodine)
Colours
• All halogens have distinct colours which get darker going down the group

The colours of the Group 17 elements get darker going down the group
Volatility
• Volatility refers to how easily a substance can evaporate
o A volatile substance will have a low boiling point

The boiling points of the Group 17 elements increase going down the group which indicates
that the elements become less volatile
 • Going down the group, the boiling point of the elements increases which means that the
volatility of the halogens decreases
o This means that fluorine is the most volatile and iodine the least volatile
Group 17: Trends in Bond Strength
• Halogens are diatomic molecules in which covalent bonds are formed by overlapping
their orbitals
• In a covalent bond, the bonding pair of electrons is attracted to the nuclei on either side
and it is this attraction that holds the molecule together
• Going down the group, the atomic size of the halogens increases
• The bonding pair of electrons get further away from the halogen nucleus and are
therefore less strongly attracted towards in

A covalent bond is formed by the orbital overlap of two atoms and the attraction of electrons
towards the nuclei; The bigger the atom, the weaker the covalent bond

• The bond strength of the halogen molecules therefore decreases going down the group

The bond enthalpies decrease indicating that the bond strengths decrease going down the
group
• Bond enthalpy is the heat needed to break one mole of a covalent bond
• The higher the bond enthalpy, the stronger the bond
• An exception to this is fluorine which has a smaller bond enthalpy than chlorine and
bromine
 • Fluorine is so small that when two atoms of fluorine get together their lone pairs get so
close that they cause significant repulsion counteracting the attracting between the
bonding pair of electrons and two nuclei

The lone pairs on fluorine get so close to each other in a fluorine molecule that they cause
repulsion which decreases the bond strength
Group 17: Dipole Forces & Volatility
• Halogens are non-metals and are diatomic molecules at room temperature
o This means that they exist as molecules which are made up of two similar atoms,
such as F2
• The halogens are simple molecular structures with weak van der Waals’ forces
between the diatomic molecules caused by instantaneous dipole-induced dipole forces

The diagram shows that a sudden distribution of electrons in a nonpolar molecule can cause
an instantaneous dipole. When this molecule gets close to another non-polar molecule it can
induce a dipole as the cloud of electrons repel the electrons in the neighbouring molecule to
the other side
 • The more electrons there are in a molecule, the greater the instantaneous dipole-induced
dipole forces
• Therefore, the larger the molecule the stronger the van der Waals’ forces between
molecules
• This is why as you go down the group, it gets more difficult to separate the molecules and
the melting and boiling points increase
• As it gets more difficult to separate the molecules, the volatility of the halogens
decreases going down the group

Going down the group, the van der Waals’ forces increase due to an increased number of
electrons in the molecules which means that the volatility decreases

8.2 The chemical properties of the halogen elements and the hydrogen halides
Group 17: Oxidising Agents
• Halogens react with metals by accepting an electron from the metal atom to become an
ion with 1- charge
Eg. Ca(s) + Cl2(g) → Ca2+(Cl–)2(s)
• Halogens are therefore oxidising agents:
o Halogens oxidise the metal by removing an electron from the metal (the oxidation
number of the metal increases)
o Halogens become reduced as they gain an extra electron from the metal atom (the
oxidation number of the halogen decreases)
• The oxidising power of the halogens decreases going down the group (the halogens get
less reactive)
• This can be explained by looking at their electronegativities:
 The electronegativity of the halogens decreases going down the group
• The electronegativity of an atom refers to how strongly it attracts electrons towards itself
in a covalent bond
• The decrease in electronegativity is linked to the size of the halogens
• Going down the group, the atomic radii of the elements increase which means that the
outer shells get further away from the nucleus
• An ‘incoming’ electron will therefore experience more shielding from the attraction of
the positive nuclear charge
• The halogens’ ability to accept an electron (their oxidising power) therefore decreases
going down the group

With increasing atomic size of the halogens (going down the group) their electronegativity,
and therefore oxidising power, decreases
• The reactivity of halogens is also shown by their displacement reactions with other
halide ions in solutions
 • A more reactive halogen can displace a less reactive halogen from a halide solution of
the less reactive halogen
o Eg. The addition of chlorine water to a solution of bromine water:
Cl2(aq) + 2NaBr(aq) → 2NaCl(aq) + Br2(aq)
•
o The chlorine has displaced the bromine from solution as it is more reactive which
can be summarised in the following ionic equation:
Cl2(aq) + 2Br–(aq) → 2Cl–(aq) + Br2(aq)

Group 17: Reaction with Hydrogen

• Halogens react with hydrogen gas to form hydrogen halides
• Due to the decrease in reactivity of the halogens going down the group, the reactions
between halogen and hydrogen gas become less vigorous
• The table below shows a summary of the reaction between halogen and hydrogen gas

Reaction between halogen & hydrogen gas

Thermal Stability of the Hydrogen Halides

• Thermal stability refers to how well a substance can resist breaking down when heated
o A substance that is thermally stable will break down at high temperatures
• The hydrogen halides formed from the reaction of halogen and hydrogen gas decrease in
thermal stability going down the group
• The decrease in thermal stability can be explained by looking at the bond energies of the
hydrogen-halogen bond
o Going down the group, the atomic radius of the halogens increases
o The overlap of its outer shell with a hydrogen atom therefore gives a longer bond
length
o The longer the bond, the weaker it is, and the less energy required to break it
• As the bonds get weaker, the hydrogen halogens become less stable to heat going down
the group
 The thermal stability of the hydrogen halide decreases going down the group as their bonds
become weaker due to the increased atomic radius of the halogens

8.3 Some reactions of the halide ions

Halide Ions: Reducing Agents

• Halide ions can also act as reducing agents and donate electrons to another atom
• The halide ions themselves get oxidised and lose electrons
• The reducing power of the halide ions increases going down the group
• This trend can be explained by looking at the ionic radii of the halides’ ions

The diagram shows that going down the group the ionic radii of the halogens increases

• Going down the group, the halide ions become larger

• The outermost electrons get further away from the nucleus
• The outermost electrons also experience more shielding by inner electrons
• As a result of this, the outermost electrons are held less tightly to the positively charged
nucleus
 • Therefore, the halide ions lose electrons more easily going down the group and their
reducing power increases

The reducing power of the halide ions increases going down the group

Reactions of Halide Ions

Silver ions & ammonia
• Halide ions can be identified in an unknown solution by dissolving the solution in nitric
acid and then adding a silver nitrate solution followed by ammonia solution
• The halide ions will react with the silver nitrate solution as follows:
AgNO3(aq) + X–(aq) → AgX(s) + NO3–(aq)
(general equation)
Ag (aq) + X–(aq) → AgX(s)
+

(ionic equation)

o X– is the halide ion in both equations

• If the unknown solution contains halide ions, then a precipitate of the silver halide will
be formed (AgX)
A silver halide precipitate is formed upon addition of silver nitrate solution to halide ion
solution

• Dilute followed by concentrated ammonia is added to the silver halide solution to

identify the halide ion
• If the precipitate dissolves in dilute ammonia the unknown halide is chloride
• If the precipitate does not dissolve in dilute but in concentrated ammonia the unknown
halide is bromide
• If the precipitate does not dissolve in dilute nor concentrated ammonia the unknown
halide is iodide

Silver chloride and silver bromide precipitates dissolve on addition of ammonia solution
whereas silver iodide doesn’t
Reaction of halide ions with silver nitrate & ammonia solutions table

Concentrated sulfuric acid

• Chloride, bromide and iodide ions react with concentrated sulfuric acid to produce toxic
gases
• These reactions should therefore be carried out in a fume cupboard
• The general reaction of the halide ions with concentrated sulfuric acid is:
H2SO4(l) + X–(aq) → HX(g) + HSO4–(aq)
(general equation)
Where X– is the halide ion
Reaction of chloride ions with concentrated sulfuric Acid
• Concentrated sulfuric acid is dropwise added to sodium chloride crystals to produce
hydrogen chloride gas

Apparatus set up for the reaction of sodium chloride with concentrated sulfuric acid
 • The reaction that takes place is:
H2SO4(l) + NaCl(s) → HCl(g) + NaHSO4(s)
• The HCl gas produces is seen as white fumes
Reaction of bromide ions with concentrated sulfuric acid
• The thermal stability of the hydrogen halides decreases down the group
• The reaction of sodium bromide and concentrated sulfuric acid is:
H2SO4(l) + NaBr(s) → HBr(g) + NaHSO4(s)
• The concentrated sulfuric acid oxidises HBr which decomposes into bromine and
hydrogen gas and sulfuric acid itself is reduced to sulfur dioxide gas:
2HBr(g) + H2SO4(l) → Br2(g) + SO2(g) + 2H2O(l)
• The bromine is seen as a reddish-brown gas
Reaction of iodide ions with concentrated sulfuric acid
• The reaction of sodium iodide and concentrated sulfuric acid is:
H2SO4 (l) + NaI (s) → HI (g) + NaHSO4 (s)
• Hydrogen iodide decomposes the easiest
• Sulfuric acid oxidises the hydrogen iodide to several extents:
• The concentrated sulfuric acid oxidises HI and is itself reduced to sulfur dioxide gas:
2HI (g) + H2SO4 (l) → I2 (g) + SO2 (g) + 2H2O (l)
• Iodine is seen as a violet/purple vapour
• The concentrated sulfuric acid oxidises HI and is itself reduced to sulfur:
6HI (g) + H2SO4 (l) → 3I2 (g) + S (s) + 4H2O (l)
• Sulfur is seen as a yellow solid
• The concentrated sulfuric acid oxidises HI and is itself reduced to hydrogen sulfide:
8HI (g) + H2SO4 (l) → 4I2 (g) + H2S (s) + 4H2O (l)
• Hydrogen sulfide has a strong smell of bad eggs

Halide ion reactions with concentrated sulfuric acid table

8.4 The reactions of chlorine
Reaction of Chlorine
• A disproportionation reaction is a reaction in which the same species is both oxidised
and reduced
• The reaction of chlorine with dilute alkali is an example of a disproportionation reaction
• In these reactions, the chlorine gets oxidised and reduced at the same time
• Different reactions take place at different temperatures of the dilute alkali
Chlorine in cold alkali (15 oC)
• The reaction that takes place is:

• The ionic equation is:

• The ionic equation shows that the chlorine gets both oxidised and reduced
• Chlorine gets oxidised as there is an increase in ox. no. from 0 to +1 in ClO–(aq)
o The half-equation for the oxidation reaction is:

• Chlorine gets reduced as there is a decrease in ox. no. from 0 to -1 in Cl–(aq)

o The half-equation for the reduction reaction is:

Chlorine in hot alkali (70 oC)

• The reaction that takes place is:

• The ionic equation is:

• The ionic equation shows that the chlorine gets both oxidised and reduced
• Chlorine gets oxidised as there is an increase in ox. no. from 0 to +5 in ClO3–(aq)
o The half-equation for the oxidation reaction is:
 • Chlorine gets reduced as there is a decrease in ox. no. from 0 to -1 in Cl–(aq)
o The half-equation for the reduction reaction is:

Chlorine in Water Purification

• Chlorine can be used to clean water and make it drinkable
• The reaction of chlorine in water is a disproportionation reaction in which the chlorine
gets both oxidised and reduced

The disproportionation reaction of chlorine with water in which chlorine gets reduced to HCl
and oxidised to HClO
• Chloric(I) acid (HClO) sterilises water by killing bacteria
• Chloric acid can further dissociate in water to form ClO–(aq):
HClO(aq) → H+(aq) + ClO–(aq)
• ClO–(aq) also acts as a sterilising agent cleaning the water

Exam Tip
Adding chlorine to a water supply is an effective way to make the water safe to drink as it
forms the sterilising agent HClO which in turn dissociates in water into another sterilising
agent, ClO–(aq)

Summary
• The halogens chlorine, bromine and iodine exist as covalent diatomic molecules. They
become increasingly less volatile and more deeply coloured on descending Group 17. The
volatility decreases as van der Waals’ forces between molecules increase.
• All the halogens are oxidising agents. Fluorine is the strongest oxidising agent and iodine is
the weakest.The reactivity of the halogens decreases on descending the group.
• It gets easier to oxidise the hydrogen halides going down Group 17 as the strength of the
hydrogen–halogen bond decreases.
• Chlorine reacts with cold hydroxide ions in a disproportionation (‘self reduction-oxidation’)
reaction. This reaction produces commercial bleach.
• A different disproportionation reaction takes place between chlorine and hot alkali,
producing NaCl(aq), NaClO3(aq) and water.
• The halogens all have important industrial uses, especially chlorine, which is used in the
manufacture of many other useful products. Possibly the most important use of chlorine is in
the prevention of disease by chlorination of water supplies.
CHAPTER 9
NITROGEN AND SULFUR
Learning Objectives:
9.1 Nitrogen and sulfur

Learning Outcomes:
Candidates should be able to:

→ Explain the lack of reactivity of nitrogen, with reference to triple bond strength and lack of
polarity
→ Describe and explain:
(a) the basicity of ammonia, using the Brønsted–Lowry theory
(b) the structure of the ammonium ion and its formation by an acid–base reaction
(c) the displacement of ammonia from ammonium salts by an acid–base reaction
→ State and explain the natural and man-made occurrences of oxides of nitrogen and their catalytic
removal from the exhaust gases of internal combustion engines
→ Understand that atmospheric oxides of nitrogen (NO and NO₂) can react with unburned
hydrocarbons to form peroxyacetyl nitrate, PAN, which is a component of photochemical smog
→ Describe the role of NO and NO₂ in the formation of acid rain both directly and in their
catalytic role in the oxidation of atmospheric sulfur dioxide
 INTRODUCTION:
The Group 15 element nitrogen makes up nearly four-fifths of the atmosphere on Earth.
Nitrogen is a vital element in many of the processes of life, but as a pure gas it is unreactive. For
this reason, nitrogen gas helps to prevent explosions when crude oil is pumped into or out of super-
tankers, when the volatile fuel vapours can mix with oxygen from the air.
Sulfur is a Group 16 element that is mined for the production of sulfuric (VI) acid, one of the
most important industrial chemicals, used in the manufacture of paints, dyes, plastics and fibres.

a Nitrogen gas is used in the hold of oil tankers above the crude oil as it is pumped ashore. This
unreactive gas helps to prevent the chance of an explosive mixture of crude oil vapour and air
forming inside the tanker. b Sulfur can be mined from underground deposits by pumping down
super-heated water to melt the sulfur (it melts at about 115 °C). The molten sulfur is then forced
to the surface under pressure and allowed to solidify back into a brittle, yellow solid. The
‘crown-shaped’ sulfur molecules, S₈, can pack together in regular patterns, forming crystals.

9.1 Nitrogen and Sulfurs

Reactivity of Nitrogen
• Nitrogen is a diatomic molecule and the main unreactive gas in air
• 78% of air is nitrogen gas
• The lack of reactivity of nitrogen gas can be explained by looking at its intramolecular
bonds
• Intramolecular bonds are the bonds within a molecule
Bonding in nitrogen
• The electron configuration of a nitrogen atom is 1s2 2s2 2p3
• To achieve a full outer shell of electrons, it needs to gain three electrons
• Nitrogen atoms therefore form a triple covalent bond between two nitrogen atoms in
which they share three electrons with each other

The diagram shows a triple covalent bond between two nitrogen atoms to achieve a full outer
shell of electrons
 • The bond enthalpy of the nitrogen triple bond is 1000 kJ mol-1
• This means that 1000 kJ of energy is needed to break one mole of N2 triple bond
• As it is so difficult to break the nitrogen triple bond, nitrogen and oxygen gas in air will
not react with each other
• Only under extreme conditions will nitrogen gas react (eg. during a thunderstorm)
Polarity of nitrogen
• The electrons in a nitrogen molecule are shared equally between the two nitrogen atoms
• Therefore, nitrogen molecules are nonpolar molecules

Since the electronegativity of the two nitrogen atoms is the same, the will pull the electrons
towards them equally so overall the molecule is nonpolar

• Due to the lack of polarity, nitrogen gas is not attracted to or likely to react with other
molecules the way polar molecules would
Properties of Ammonia
• Ammonia is a compound of nitrogen and will turn damp red litmus paper blue as it is an
alkaline gas
• Ammonia is made on a large scale in industry using the Haber process:
N2(g) + 3H2(g) ⇌ 2NH3(g)
Basicity of ammonia
• Ammonia can act as a Brønsted–Lowry base by accepting a proton (H+) using the lone
pair of electrons on the nitrogen atom to form an ammonium ion:
NH3(aq) + H+(aq) → NH4+(aq)
• In an aqueous solution of ammonia, an equilibrium mixture is established
NH3(aq) + H2O(l) ⇌ NH4+(aq) + OH–(aq)
• Since the position of the equilibrium lies well over to the left the ammonia solution is
only weakly alkaline
• There is a higher concentration of ammonia molecules than hydroxide ions in solution
• Ammonia is therefore a weak base
Structure & formation of ammonium ion
• The ammonium ion is formed by an acid-base reaction of ammonia with water:
NH3(aq) + H2O(l) ⇌ NH4+(aq) + OH–(aq)
• The nitrogen in ammonia is covalently bonded to three hydrogen atoms and has one lone
pair of electrons causing the ammonia molecule to have a pyramidal shape
 Ammonia has a pyramidal shape due to its lone pair of electrons
• The nitrogen atom in ammonia uses its lone pair of electrons to form a dative bond with a
proton to form the ammonium ion
• The ammonium ion has a tetrahedral shape in which all bonds have the same length

The tetrahedral shape of the ammonium ion

Preparation of ammonia gas from an ammonium salt
• Ammonia gas can be prepared from an ammonium salt and a base in an acid-base
reaction:

• Ammonium chloride (NH4Cl) and calcium hydroxide (Ca(OH)2) are mixed together and
then heated
• NH4+ acts as an acid (proton donor) and OH– acts as a base (proton acceptor)
• This acid-base reaction can be used to test if an unknown solution contains ammonium
ions
• If the unknown solution does contain ammonium ions, it will react with calcium
hydroxide to form ammonia gas
• This ammonia gas will turn damp red litmus paper blue
 The diagram shows the apparatus set up for the preparation of ammonia gas from an
ammonium salt and calcium hydroxide
Oxides of Nitrogen
Natural occurrence of nitrogen oxides
• Due to its lack of reactivity, only under extreme conditions will nitrogen react with
oxygen to form gaseous nitrogen oxides
• An example of these extreme conditions is lightning which can trigger the formation of
nitrogen(II) and nitrogen(IV) oxides (NO and NO2 respectively)
• The chemical equations for these reactions are:
N2(g) + O2(g) → 2NO(g)
N2(g) + 2O2(g) → 2NO2(g)
Man-made occurrence of nitrogen oxides
• In the engine of a car, a mixture of air and fuel is compressed and ignited by a spark
• Air consists of 78% of nitrogen and 21% of oxygen
• Under the high pressure and temperature inside a car engine, nitrogen can react with
oxygen to form nitrogen oxides
• These nitrogen oxides are released into the atmosphere through the car’s exhaust fumes
Catalytic removal of nitrogen oxides
• The nitrogen oxides released through cars’ exhaust fumes pollute the atmosphere
• Many car exhaust systems are therefore fitted with catalytic converters to reduce the
pollutants from motor vehicles
• The nitrogen oxides are reduced on the surface of the hot catalyst (eg. platinum) to form
the unreactive and harmless nitrogen gas which is then released from the vehicle’s
exhaust pipe into the atmosphere
• The chemical reaction for the reduction of nitrogen oxide to nitrogen gas by the catalyst
is as follows:
2CO(g) + 2NO(g) → 2CO2(g) + N2(g)
 A catalytic converter helps reduce the pollutants from motor vehicles

Oxides of Nitrogen & Photochemical Smog

• Nitrogen oxides are examples of primary pollutants because they are given off directly
into the air from the source of pollution
• Examples of pollution sources are car exhausts and power plants
• Nitrogen oxides are extra dangerous as they can react with substances in the air to make
secondary pollutants
• These are pollutants that are not given off directly into the air from human activity
• Exhaust fumes contain another primary pollutant called volatile organic compound
(VOCs)
• These are unburnt hydrocarbons from fuel and their oxidised products
• VOCs react with nitrogen oxides in air to form peroxyacetyl nitrate (PAN,
CH3CO3NO2)
• Sunlight provides the energy needed to start off the reactions of VOCs and nitrogen
oxides in air, so they are also called photochemical reactions
• PAN is one of the harmful pollutants found in photochemical smog
• ‘Smog’ is derived from ‘smoke’ and ‘fog’
• PAN affects the lungs and eyes and in high concentrations plant-life
Primary & secondary pollutant types & their pollution source table
 The diagram shows the formation of PAN from the photochemical reaction between VOCs
and nitrogen oxide
Oxides of Nitrogen & Acid Rain
Formation of acid rain by nitrogen oxides
• As mentioned earlier, lightning strikes trigger the formation of nitrogen(II) and nitrogen
(IV) oxides in air:
2NO(g) + O2(g) ⇌ 2NO2(g)
• The air also contains oxygen and tiny droplets of water that make up clouds
• The nitrogen(IV) oxide (NO2) dissolves and reacts in water with oxygen as follows:
NO2(aq) + H2O(l) + 1½O2(g) → 2HNO3(aq)
• When the clouds rise, the temperature decreases, and the droplets get larger
• When the droplet containing dilute nitric acid are heavy enough, they will fall down as
acid rain
 The diagram shows the formation of acid rain by the oxidation of nitrogen(IV) oxide
Nitrogen oxide as a catalyst
• Acid rain also contains dilute sulfuric acid (H2SO4)
• Sulfur(IV) oxide (SO2) is another pollutant found in the atmosphere
• When SO2 is oxidised, it forms SO3 which reacts with rainwater to form dilute sulfuric
acid as follows:
SO3(g) + H2O(l) → H2SO4(aq)
• Nitrogen oxides can directly cause acid rain but can also act as catalysts in the formation
of acid rain
• NO2 catalyses the oxidation of SO2 to SO3:
NO2(g) + SO2(g) → SO3(g) + NO(g)
•
o The formed NO gets oxidised to regenerate NO2:
NO(g) + ½ O2(g) → NO2(g)
• The regenerated NO2 molecule can get again oxidise another SO2 molecule to SO3 which
will react with rainwater to form H2SO4

The formation of dilute sulfuric acid is catalysed by the nitrogen oxides

Summary
• Nitrogen, N2, is a very unreactive gas because of the high bond energy of the N N triple
bond.
• Ammonia, NH3, is a common compound of nitrogen. An ammonia molecule can act as a
base, accepting an H+ ion to form an ammonium ion, NH4+.
• Ammonia is manufactured in the Haber process:

• Most ammonia is used to make ammonium salts in neutralisation reactions with different
acids. The salts, such as ammonium nitrate, NH4NO3, are used as fertilisers,
• Excess fertiliser can be leached out of soils into rivers and lakes, where it causes
eutrophication, killing aquatic life.
• Nitrogen oxides are formed naturally during lightning strikes, when nitrogen gas is
oxidised. These gaseous oxides are also formed in internal combustion engines and become
pollutants in the atmosphere, contributing to acid rain.
• Sulfur can be mined as the element and is used as a raw material for manufacturing sulfuric
acid in the Contact process.
• Sulfur dioxide is the main cause of acid rain. Its oxidation to sulfur trioxide is catalysed by
oxides of nitrogen.
• Acid rain causes the death of aquatic wildlife in rivers and lakes, kills trees and damages
buildings and other structures.
 INTRODUCTION:

CHAPTER 10used to decolourise glass and to depolarise dry electrochemical cells.

The element manganese is used to form many alloys, for example adding hardness to steel.
Manganese(IV) oxide is
Manganese(II) oxide is a powerful oxidising agent. One of the most useful aspects of manganese is

ELECTROCHEMISTRY
that it can exist in a number of oxidation states

a manganese(0), the metal; b manganese(II) as Mn²⁺(aq) ions; c manganese(III) as n³⁺(aq)

ions; d manganese(IV) as MnO₂; e Mn(VI) as MnO₄²⁻ as with parts b and c ions; f Mn(VII) as
MnO₄⁻as with parts b and c ions. Manganese metal is a good reductant, whereas MnO₄⁻ (aq) in
acidic solution is a good oxidant.

Learning Objectives:
10.1 Redox processes: electron transfer and changes in oxidation number (oxidation state)
10.2 Electrolysis

Learning Outcomes:
Candidates should be able to:

→ Calculate oxidation numbers of elements in compounds and ions

→ Use changes in oxidation numbers to help balance chemical equations
→ Explain and use the terms redox, oxidation, reduction and disproportionation in terms of
electron transfer and changes in oxidation number
→ Explain and use the terms oxidising agent and reducing agent
→ Use a Roman numeral to indicate the magnitude of the oxidation number of an element
→ Predict the identities of substances liberated during electrolysis from the state of electrolyte
(molten or aqueous), position in the redox series (electrode potential) and concentration
→ Sstate and apply the relationship F = Le between the Faraday constant, F, the Avogadro constant,
L, and the charge on the electron, e
→ Calculate:
10.1 Redox processes: electron transfer and changes in oxidation number
(oxidation state)
Oxidation Numbers
• The oxidation numbers (also known as oxidation state) is a number given to each atom or
ion in a compound to keep track of how many electrons they have
• In a single ion or molecular ion, the oxidation number tells us how many electrons have
been lost or gained
• Positive oxidation number = loss of electrons
• Negative oxidation number = gain of electrons
Oxidation number rules
• The oxidation number (ox.no.) refers to a single atom in a compound
Worked example: Deducing oxidation numbers

Answer
Balancing Redox Reactions
• Oxidation numbers can be used to balance chemical equations
• Roman numerals between brackets are used to show the ox. no. of an atom that can have
multiple oxidation states, eg:
Fe(III) = iron with ox. no. +3

Worked example: Writing overall redox reactions

Answer
• Step 1: Write the unbalanced equation and identify the atoms which change in ox. no.

• Step 2: Deduce the ox.no. changes

• Step 3: Balance the ox.no. changes

• Step 4: Balance the charges

• Step 5: Balance the atoms

Redox & Disproportionation Reactions
Oxidation
• Oxidation is the gain of oxygen, eg:
Cu + H2O → CuO + H2
(Cu has gained an oxygen and is oxidised)
• Oxidation is also the loss of a hydrogen, eg:
2NH3 + 3Br2 → N2 + 6HBr
(N has lost a hydrogen and is oxidised)
• Oxidation is also the loss of electrons, eg:
Cu2+ → Mg → Mg2+ + Cu
(Mg has lost two electrons and is oxidised)
• Oxidation causes an increase in ox. no., eg:
Cu2+ + Mg → Mg2+ + Cu
(change in ox. no. of Mg is +2 thus Mg is oxidised)
Reduction
• Reduction is the loss of oxygen, eg:
Cu+ H2O → 2CuO + H2
(O has been reduced)
• Reduction is also the gain of a hydrogen, eg:
2NH3+ 3Br2 → N2 + 6HBr
(Br has been reduced)
• Reduction is also the gain of electrons, eg:
Cu2+ + Mg → Mg2+ + Cu
(Cu has been reduced)
• Reduction causes a decrease in oxidation number, eg:
Cu2+ + Mg → Mg2+ + Cu
(change in ox. no. of Cu is -2 thus Cu is reduced)

Use the acronym “Oil Rig” to help you remember the definitions of oxidation and
reduction

Redox reactions
• Redox reactions are reactions in which oxidation and reduction take place together
• While one species is oxidising, another is reducing in the same reaction, eg:
Cu2++ Mg → Mg2+ + Cu
(Cu has been reduced and Mg has been oxidised)

Worked example: Oxidation and reduction

Answer
Answer 1:
Oxidised: Cl– as the ox. no. has increased by 1
Reduced: Na+ as the ox. no. has decreased by 1
Answer 2:
Oxidised: Mg as the ox. no. has increased by 2
Reduced: Fe2+ as the ox. no. has decreased by 2
Answer 3:
Oxidised: C as it has gained oxygen
Reduced: Ag as it has lost oxygen
Disproportionation reactions
• A disproportionation reaction is a reaction in which the same species is both oxidised
and reduced

Example of a disproportion reaction in which the same species (chlorine in this case) has been
both oxidised and reduced

Worked example: Balancing disproportionation reactions

Answer
• Step 1: Write the unbalanced equation and identify the atoms that change in ox. no.

• Step 2: Deduce the ox. no. changes

 • Step 3: Balance the ox. no. changes

• Step 4: Balance the charges

• Step 5: Balance the atoms

Balancing Redox Reactions

• Oxidation numbers can be used to balance chemical equations
• Roman numerals between brackets are used to show the ox. no. of an atom that can have
multiple oxidation states, eg:
Fe(III) = iron with ox. no. +3

Worked example: Writing overall redox reactions

Answer
• Step 1: Write the unbalanced equation and identify the atoms which change in ox. no.

• Step 2: Deduce the ox.no. changes

• Step 3: Balance the ox.no. changes

• Step 4: Balance the charges

• Step 5: Balance the atoms

Redox & Disproportionation Reactions

Oxidation
• Oxidation is the gain of oxygen, eg:
Cu + H2O → CuO + H2
(Cu has gained an oxygen and is oxidised)
• Oxidation is also the loss of a hydrogen, eg:
2NH3 + 3Br2 → N2 + 6HBr
 (N has lost a hydrogen and is oxidised)
• Oxidation is also the loss of electrons, eg:
Cu2+ → Mg → Mg2+ + Cu
(Mg has lost two electrons and is oxidised)
• Oxidation causes an increase in ox. no., eg:
Cu2+ + Mg → Mg2+ + Cu
(change in ox. no. of Mg is +2 thus Mg is oxidised)
Reduction
• Reduction is the loss of oxygen, eg:
Cu+ H2O → 2CuO + H2
(O has been reduced)
• Reduction is also the gain of a hydrogen, eg:
2NH3+ 3Br2 → N2 + 6HBr
(Br has been reduced)
• Reduction is also the gain of electrons, eg:
Cu2+ + Mg → Mg2+ + Cu
(Cu has been reduced)
• Reduction causes a decrease in oxidation number, eg:
Cu2+ + Mg → Mg2+ + Cu
(change in ox. no. of Cu is -2 thus Cu is reduced)

Use the acronym “Oil Rig” to help you remember the definitions of oxidation and
reduction
Redox reactions
• Redox reactions are reactions in which oxidation and reduction take place together
• While one species is oxidising, another is reducing in the same reaction, eg:
Cu2++ Mg → Mg2+ + Cu
(Cu has been reduced and Mg has been oxidised)

Worked example: Oxidation and reduction

Answer
Answer 1:
Oxidised: Cl– as the ox. no. has increased by 1
Reduced: Na+ as the ox. no. has decreased by 1
Answer 2:
Oxidised: Mg as the ox. no. has increased by 2
Reduced: Fe2+ as the ox. no. has decreased by 2
Answer 3:
Oxidised: C as it has gained oxygen
Reduced: Ag as it has lost oxygen

Disproportionation reactions
• A disproportionation reaction is a reaction in which the same species is both oxidised
and reduced

Example of a disproportion reaction in which the same species (chlorine in this case) has been
both oxidised and reduced

Worked example: Balancing disproportionation reactions

Answer
• Step 1: Write the unbalanced equation and identify the atoms that change in ox. no.

• Step 2: Deduce the ox. no. changes

 • Step 3: Balance the ox. no. changes

• Step 4: Balance the charges

• Step 5: Balance the atoms

10.2 Electrolysis
Electrolytic cells
Electrolysis is the decomposition of a compound into its elements by an electric current. It is often used
to extract metals that are high in the reactivity series. These metals cannot be extracted by heating their
ores with carbon. Electrolysis is also used to produce non-metals such as chlorine and to purify some
metals. Electrolysis is generally carried out in an electrolysis cell.
The main parts of an electrolysis cell. The actual structure of the cell will vary according to the element
extracted. The e⁻ shows the direction of travel of the electrons around the external circuit.
In the electrolysis cell:
❖ the electrolyte is the compound that is decomposed; it is either a molten ionic compound or a
concentrated aqueous solution of ions
❖ the electrodes are rods, made from either carbon (graphite) or metal, which conduct electricity to
and from the electrolyte
o the anode is the positive electrode
o the cathode is the negative electrode
❖ the power supply must be direct current.

Redox Reactions in Electrolysis

During electrolysis, the positive ions (cations) move to the cathode. When they reach the
cathode they gain electrons from the cathode. For example:

Gain of electrons is reduction. Reduction always occurs at the cathode. If metal atoms are
formed, they may be deposited as a layer of metal on the cathode. Alternatively they may form a
molten layer in the cell. If hydrogen gas is formed, it bubbles off.
The negative ions (anions) move to the anode. When they reach the anode they lose electrons to
the anode. For example:

Loss of electrons is oxidation. Oxidation always occurs at the anode.

Electrolysis is a redox reaction. For example, when molten zinc chloride is electrolysed the
electrode reactions are:

The electron loss at the anode balances the electron gain at the cathode. Overall, the reaction is:
Quantitative Electrolysis
The mass of substance deposited during electrolysis The mass of a substance produced at an
electrode during electrolysis is proportional to:
❖ the time over which a constant electric current passes
❖ the strength of the electric current.
Combining current and time, we get the relationship:

The mass of a substance produced at (or removed from) an electrode during electrolysis is
proportional to the quantity of electricity (in coulombs) which passes through the electrolyte.
The quantity of electricity is often expressed in terms of a unit called the Faraday (symbol F). 1
Faraday is the quantity of electric charge carried by 1 mole of electrons or 1 mole of singly
charged ions. Its value is 96 500 C mol⁻¹(to 3 significant figures).
During the electrolysis of silver nitrate solution, silver is deposited at the cathode:

1 Faraday of electricity (96 500 C) is required to deposit 1 mole of silver.

During the electrolysis of copper(II) sulfate solution, copper is deposited at the cathode:

The equation shows that 2 moles of electrons are needed to produce 1 mole of copper from Cu²⁺
ions. So it requires 2 Faradays of electricity (2 × 96 500 C) to deposit 1 mole of copper.
During the electrolysis of molten sodium chloride, chlorine is produced at the anode:

The equation shows that 2 moles of electrons are released when 1 mole of chlorine gas is formed
from 2 moles of Cl⁻ ions. So it requires 2 Faradays of electricity (2 × 96 500 C) to produce 1
mole of Cl₂.
During the electrolysis of an aqueous solution of sulfuric acid or aqueous sodium sulfate, oxygen
is produced at the anode:
The equation shows that 4 moles of electrons are released when 1 mole of oxygen gas is formed
from 4 moles of OH⁻ ions. So it requires 4 Faradays of electricity (4 × 96 500 C) to produce 1
mole of O₂.
Calculating Amount Of Substance Produced During Electrolysis
We can use the value of F to calculate:
❖ the mass of substance deposited at an electrode
❖ the volume of gas produced at an electrode.
Worked Example:
Calculate the mass of lead deposited at the cathode during electrolysis when a current of 1.50 A
flows through molten lead(II) bromide for 20.0 min. (Ar value: [Pb] = 207; F = 96 500 C mol–1)
Step 1 Write the half-equation for the reaction.

Step 2 Find the number of coulombs required to deposit 1 mole of product at the electrode. 2
moles of electrons are required per mole of Pb formed
= 2F
= 2 × 96 500
= 193 000 C mol⁻¹
Step 3 Calculate the charge transferred during the electrolysis.
Q =I×t
= 1.50 × 20 × 60
= 1800 C
Step 4 Calculate the mass by simple proportion using the relative atomic mass.

Calculating the Avogadro constant by an electrolytic method

The Avogadro constant, L, is the number of specified particles in 1 mole. We can use an
electrolytic method to find a value for the Avogadro constant by calculating the charge
associated with 1 mole of electrons.

We can calculate the charge on the electron by experiment. The results show us that the charge
on the electron is approximately 1.60 × 10–19 C.
Finding the charge on 1 mo le of electrons
The charge on 1 mole of electrons can be found from a simple electrolytic experiment. The
apparatus for this is shown below:

Apparatus for calculating the mass of copper deposited during the electrolysis of aqueous
copper(II) sulfate.

The procedure is:

❖ weigh the pure copper anode and pure copper cathode separately
❖ arrange the apparatus as shown in Figure; the variable resistor is used to keep the current
constant
❖ pass a constant electric current for a measured time interval
❖ remove the cathode and anode and wash and dry them with distilled water and then with
propanone
❖ reweigh the cathode and anode.
The cathode increases in mass because copper is deposited. The anode decreases in mass because
the copper goes into solution as copper ions. The decrease in mass of the anode is measured.
This is preferred because the copper does not always ‘stick’ to the cathode very well.
A sample calculation is shown below, using a current of 0.20 A for 34 min.
❖ mass of anode at start of the experiment = 56.53 g
❖ mass of anode at end of experiment = 56.40 g
❖ mass of copper removed from anode = 0.13 g
❖ quantity of charge passed Q = I × t
= 0.20 × 34 × 60
 = 408 C
To deposit 0.13 g of copper requires 408 C, so to deposit 1 mole of copper (63.5 g) requires

But the equation for the electrolysis shows that 2 moles of electrons are needed to produce 1
mole of copper:

This is in good agreement with the accurate value of 6.02 × 1023 mol⁻¹.
 Summary
• An electrolytic cell consists of a direct current power supply connected to two electrodes
which dip into an electrolyte.
• An electrolyte is a compound that is decomposed during electrolysis.
• During electrolysis reduction occurs at the cathode (negative electrode) because ions gain
electrons from the cathode.
• During electrolysis oxidation occurs at the anode (positive electrode) because ions lose
electrons to the anode.
• The Faraday constant (F) is the electric charge, in coulombs, on 1 mole of electrons.
• The relationship between the Faraday constant, the Avogadro constant (L) and the charge
on an electron (e) is given by F = Le.
• A value for the Avogadro constant can be determined by an electrolytic method using the
relationship F = Le.
• The nature of the substances liberated during electrolysis depends on:
– the state of the electrolyte (molten or aqueous); a metal is formed at the cathode
when molten metal salts are electrolysed; hydrogen may be formed at the cathode
when dilute aqueous solutions of metal salts are electrolysed
– the position of the ions (in the electrolyte) in the redox series; ions lower in the redox
series are more likely to be discharged than those higher in the series
– the concentration of the ions in the electrolyte; when different ions are not very far
apart in the redox series, the ion present in greater concentration is more likely to be
discharged.
• The quantity of charge, in coulombs, passed during electrolysis is found by multiplying
the current, in amps, by time, in seconds, Q = It.
• The mass and/or volume of substance liberated during electrolysis can be calculated from
the quantity of charge and the number of Faradays required to discharge 1 mole of ions.

End of Chapter Question

1. a. State and explain the variation in the oxidation numbers of the chlorides of the elements
Na, Mg, Al and Si! [2]
b. describe the reaction of phosphorus (V) chloride with water and write an equation for the
reaction! [2]
c. Complete the electronic configuration of the following ions [2]
Cr³⁺ : 1S²2S²2P⁶………………………………….
Mn²⁺: 1S²2S²2P⁶………………………………….
2. The diagram shows an electrochemical cell designed to find the standard electrode potential
for zinc.

a. Name the apparatus labelled a and give a characteristic it should have. [2]
b. i Name part b and give its two functions. [3]
ii Describe how part b can be prepared. [2]
c. What is c? [2]
d. Name part d and give its two functions. [3]
e. Give the three standard conditions for the measurement of a standard electrode
potential. [3]
3.
CHAPTER 11
EQUILIBRIA
Learning Objectives:
11.1 Chemical equilibria: reversible reactions, dynamic equilibrium
11.2 Brønsted–Lowry theory of acids and bases

Learning Outcomes:
Candidates should be able to:

→ (a) understand what is meant by a reversible reaction

(b) understand what is meant by dynamic equilibrium in terms of the rate of forward and reverse
reactions being equal and the concentration of reactants and products remaining constant
(c) understand the need for a closed system in order to establish dynamic equilibrium
→ Define Le Chatelier’s principle as: if a change is made to a system at dynamic equilibrium, the
position of equilibrium moves to minimise this change
→ Use Le Chatelier’s principle to deduce qualitatively (from appropriate information) the effects of
changes in temperature, concentration, pressure or presence of a catalyst on a system at
equilibrium
→ Deduce expressions for equilibrium constants in terms of concentrations, Kc
→ Use the terms mole fraction and partial pressure
→ Deduce expressions for equilibrium constants in terms of partial pressures, Kp (use of the
relationship between Kp and Kc is not required)
→ Use the Kc and Kp expressions to carry out calculations (such calculations will not require the
solving of quadratic equations)
→ Calculate the quantities present at equilibrium, given appropriate data
→ State whether changes in temperature, concentration or pressure or the presence of a catalyst
affect the value of the equilibrium constant for a reaction
→ Describe and explain the conditions used in the Haber process and the Contact process, as
examples of the importance of an understanding of dynamic equilibrium in the chemical
industry and the application of Le Chatelier’s principle
→ State the names and formulae of the common acids, limited to hydrochloric acid, HCl, sulfuric
acid, H₂SO₄, nitric acid, HNO₃, ethanoic acid, CH₃COOH
→ State the names and formulae of the common alkalis, limited to sodium hydroxide, NaOH,
potassium hydroxide, KOH, ammonia, NH₃
Continued:
→ Describe the Brønsted–Lowry theory of acids and bases
→ Describe strong acids and strong bases as fully dissociated in aqueous solution and weak acids
and weak bases as partially dissociated in aqueous solution
→ Appreciate that water has pH of 7, acid solutions pH of below 7 and alkaline solutions pH of
above 7
→ Explain qualitatively the differences in behaviour between strong and weak acids including the
reaction with a reactive metal and difference in pH values by use of a pH meter, universal
indicator or conductivity
→ Understand that neutralisation reactions occur when H+(aq) and OH–(aq) form H2O(l)
→ Understand that salts are formed in neutralisation reactions
→ Sketch the pH titration curves of titrations using combinations of strong and weak acids with
strong and weak alkalis
→ Select suitable indicators for acid-alkali titrations, given appropriate data (pKa values will not be
used)

INTRODUCTION:
In 1863, Norwegian chemists Cato Maximilian Guldberg (1836-1902) and Peter Waage (1833-
1900)—who happened to be brothers-in-law—formulated what they called the law of mass action.
Today, this is called the law of chemical equilibrium, which states that the direction taken by a
reaction is dependant not merely on the mass of the various components of the reaction, but also
upon the concentration—that is, the mass present in a given volume.
Systems in equilibrium are balanced. For example, if you are running on a treadmill you are in
constant motion. However, you are not moving forward or backwards. As fast as you run forward
the treadmill is moving you backwards. You are in equilibrium with the treadmill.

In the same way chemical reactions can be in equilibrium (the products and reactants are produced
at the same rate). We will begin by exploring chemical equilibrium in more detail
11.1 Chemical Equilibria: Reversible Reactions, Dynamic Equilibrium
Reversible Reactions & Dynamic Equilibrium
Reversible reaction
• Some reactions go to completion where the reactants are used up to form the products
and the reaction stops when all of the reactants are used up
• In reversible reactions the products can react to reform the original reactants
• To show a reversible reaction, two opposing half arrows are used: ⇌

The diagram shows an example of a forward and backward reaction that can be written as one
equation using two half arrows
Dynamic equilibrium
• In a dynamic equilibrium the reactants and products are dynamic (they are constantly
moving)
• In a dynamic equilibrium the rate of the forward reaction is the same as the rate of the
backward reaction in a closed system, and the concentrations of the reactants and
products is constant

The diagram shows a snapshot of a dynamic equilibrium in which molecules of hydrogen

iodide are breaking down to hydrogen and iodine at the same rate as hydrogen and iodine
molecules are reacting together to form hydrogen iodide
 The diagram shows that the concentration of the reactants and products does not change
anymore once equilibrium has been reached (equilibrium was approached using reactants)

The diagram shows that the concentration of the reactants and products does not change
anymore once equilibrium has been reached (equilibrium was approached using products)
• A closed system is one in which none of the reactants or products escape from the
reaction mixture
• In an open system, matter and energy can be lost to the surroundings
• When a reaction takes place entirely in solution, equilibrium can be reached in open
flasks as a negligible amount of material is lost through evaporation
• If the reaction involves gases, equilibrium can only be reached in a closed system
 The diagram shows a closed system in which no carbon dioxide gas can escape and the
calcium carbonate is in equilibrium with the calcium oxide and carbon dioxide

The diagram shows an open system in which the calcium carbonate is continually
decomposing as the carbon dioxide is lost causing the reaction to eventually go to completion

Exam Tip
A common misconception is to think that the concentrations of the reactants and products are
equal. However, they are not equal but they remain constant at dynamic equilibrium (i.e. the
concentrations are not changing).
The concentrations will change as the reaction progresses, only until the equilibrium is reached.

Le Chatelier's Principle
Position of the equilibrium
• The position of the equilibrium refers to the relative amounts of products and reactants
in an equilibrium mixture.
• When the position of equilibrium shifts to the left, it means the concentration of
reactants increases
• When the position of equilibrium shifts to the right, it means the concentration of
products increases
Le Chatelier’s principle
• Le Chatelier’s principle says that if a change is made to a system at dynamic
equilibrium, the position of the equilibrium moves to minimise this change
• The principle is used to predict changes to the position of equilibrium when there are
changes in temperature, pressure or concentration
Effects of concentration
Effects of concentration table

Worked example: Changes in equilibrium position

Answer
Answer 1:
The position of the equilibrium moves to the left and more ethanoic acid and ethanol are formed.
The reaction moves in this direction to oppose the effect of added ethyl ethanoate, so the ethyl
ethanoate decreases in concentration.
Answer 2:
The position of the equilibrium moves to the left and more ethanoic acid and ethanol are formed.
The reaction moves in this direction to oppose the removal of ethanol so more ethanol (and
ethanoic acid) are formed from ethyl ethanoate and water.
Answer 3:
There is no effect as the water dilutes all the ions equally so there is no change in the ratio of
reactants to products.

Effects of pressure
• Changes in pressure only affect reactions where the reactants or products are gases
Effects of pressure table
Worked example: Changes in pressure

Answer
Answer 1:
The equilibrium shifts to the left as there are fewer gas molecules on the left.
This causes a decrease in pressure.
Answer 2:
The equilibrium shifts to the left as there are no gas molecules on the left but there is CO2 on the
right.
This causes a decrease in pressure.
Answer 3:
The equilibrium shifts to the right as there is a greater number of gas molecules on the right.
This causes an increase in pressure.

Effects of temperature
Effects of temperature table
Worked example: Changes in temperature

Answer
Answer 1:
The reaction will absorb the excess energy and since the forward reaction is endothermic, the
equilibrium will shift to the right.
Answer 2:
The reaction will absorb the excess energy and since this causes a shift of the equilibrium
towards the right (as more CO2(g) is formed) this means that the reaction is endothermic
(because endothermic reactions favour the products).
Effects of catalysts
• A catalyst is a substance that increases the rate of a chemical reaction (they increase the
rate of the forward and reverse reaction equally)
• Catalysts only cause a reaction to reach its equilibrium faster
• Catalysts therefore have no effect on the position of the equilibrium once

Equilibrium Constant: Concentrations

Equilibrium expression & constant
• The equilibrium expression is an expression that links the equilibrium constant, Kc, to
the concentrations of reactants and products at equilibrium taking the stoichiometry
of the equation into account
• So, for a given reaction:
aA + bB ⇌ cC + dD
the Kc is defined as follows:

Equilibrium expression linking the equilibrium concentration of reactants and products at

equilibrium
 • Solids are ignored in equilibrium expressions
• The Kc of a reaction is specific and only changes if the temperature of the reaction
changes

Worked example: Deducing equilibrium expressions

Answer

Mole Fraction & Partial Pressure

Partial pressure
• For reactions involving mixtures of gases, the equilibrium constant Kp is used as it is
easier to measure the pressure than the concentration for gases
• The partial pressure of a gas is the pressure that the gas would have if it was in the
container all by itself
• The total pressure is the sum of the partial pressure

Equation to calculate the total pressure in a mixture of gases

 The diagram shows that each gas in the mixture has a partial pressure contributing towards
the total pressure
Mole fraction
• The mole fraction of a gas is the ratio of moles of a particular gas to the total number of
moles of gas present

Equation to calculate the mole fraction of a particular gas in a gas mixture

• To calculate the partial pressures of each gas the following relationship can be used:

Equation to calculate the partial pressure of a particular gas in a gas mixture

The sum of the mole fractions should add up to 1.00, while the sum of the partial pressures
should add up to the total pressure.

Equilibrium Constant: Partial Pressures

Equilibrium expressions involving partial pressures
• Equilibrium expressions in terms of partial pressures are written similarly to those
involving concentrations with a few differences:

The diagram shows a comparison of writing equilibrium expressions in terms of partial

pressures and concentrations
Worked example: Deducing equilibrium expressions of gaseous reactions

Answer

Equilibrium Constant: Calculations

Calculations involving Kc
• In the equilibrium expression each figure within a square bracket represents the
concentration in mol dm-3
• The units of Kc therefore depend on the form of the equilibrium expression
• Some questions give the number of moles of each of the reactants and products at
equilibrium together with the volume of the reaction mixture
• The concentrations of the reactants and products can then be calculated from the number
of moles and total volume

Equation to calculate concentration from number of moles and volume

Worked example: Calculating Kc of ethanoic acid

Answer
• Step 1: Calculate the concentrations of the reactants and products

• Step 2: Write out the balanced chemical equation with the concentrations of beneath each
substance

• Step 3: Write the equilibrium constant for this reaction in terms of concentration

• Step 4: Substitute the equilibrium concentrations into the expression

• Step 5: Deduce the correct units for Kc

All units cancel out

Therefore, Kc = 4.03
• Note that the smallest number of significant figures used in the question is 3, so the final
answer should also be given to 3 significant figures
• Some questions give the initial and equilibrium concentrations of the reactants but
products
• An initial, change and equilibrium table should be used to determine the equilibrium
concentration of the products using the molar ratio of reactants and products in the
stoichiometric equation
Worked example: Calculating Kc of ethyl ethanoate

Answer
• Step 1: Write out the balanced chemical equation with the concentrations of beneath each
substance using an initial, change and equilibrium table

• Step 2: Calculate the concentrations of the reactants and products

• Step 3: Write the equilibrium constant for this reaction in terms of concentration

• Step 4: Substitute the equilibrium concentrations into the expression

= 0.28
• Step 5: Deduce the correct units for Kc

All units cancel out

Therefore, Kc = 0.288
Calculations involving Kp
• In the equilibrium expression the p represent the partial pressure of the reactants and
products in Pa
• The units of Kp therefore depend on the form of the equilibrium expression
Worked example: Calculating Kp of a gaseous reaction

Answer
• Step 1: Write the equilibrium constant for the reaction in terms of partial pressures

• Step 2: Substitute the equilibrium concentrations into the expression

= 9.1 x 10-6
• Step 3: Deduce the correct units of Kp

The units of Kp are Pa-1

Therefore, Kp = 9.1 x 10-6 Pa-1
• Some questions only give the number of moles of gases present and the total pressure
• The number of moles of each gas should be used to first calculate the mole fractions
• The mole fractions are then used to calculate the partial pressures
• The values of the partial pressures are then substituted in the equilibrium expression

Worked example: Calculating Kp of hydrogen iodide equilibrium reaction

 • Step 1: Calculate the total number of moles
Total number of moles = 1.71 x 10-3 + 2.91 x 10-3 + 1.65 x 10-2
= 2.112 x 10-2
• Step 2: Calculate the mole fraction of each gas

• Step 3: Calculate the partial pressure of each gas

H2 = 0.0810 x 100 = 8.10 kPa
I2 = 0.1378 x 100 = 13.78 kPa
HI = 0.7813 x 100 = 78.13 kPa
• Step 4: Write the equilibrium constant in terms of partial pressure

• Step 5: Substitute the values into the equilibrium expression

= 54.7
• Step 6: Deduce the correct units for Kp

All units cancel out

Therefore, Kp = 54.7
• Other questions related to equilibrium expressions may involve calculating quantities
present at equilibrium given appropriate data

Worked example: Calculating partial pressures

Answer
There are equal volumes of reactants A and B in a 1:1 molar ratio.
This means their partial pressures will be the same.
B therefore also has an equilibrium partial pressure of 0.5
Total pressure = sum of equilibrium (Σ) partial pressures
Therefore, the sum of all the partial pressures must equal to 3 atm
0.5 + 0.5 + pc = 3 atm
pc = 2 atm
Changes that Affect the Equilibrium Constant
Changes in concentration
• If all other conditions stay the same, the equilibrium constant Kc is not affected by any
changes in concentration of the reactants or products
• For example, the decomposition of hydrogen iodide:
2HI ⇌ H2 + I2
The equilibrium expression is:

Adding more HI makes the ratio of [ products ] to [ reactants ] smaller

To restore equilibrium, [H2] and [I2] increases and [HI] decreases
Equilibrium is restored when the ratio is 6.25 x 10-3 again
Changes in pressure
• A change in pressure only changes the position of the equilibrium (see Le Chatelier’s
principle)
• If all other conditions stay the same, the equilibrium constant Kc is not affected by any
changes in pressure of the reactants and products
Changes in temperature
• Changes in temperature change the equilibrium constant Kc
• For an endothermic reaction such as:

An increase in temperature:
[H2] and [I2] increases
[HI] decreases
Because [H2] and [I2] are increasing and [HI] is decreasing, the equilibrium constant Kc
increases
• For an exothermic reaction such as:

An increase in temperature:
[SO3] decreases
[SO2] and [O2] increases
Because [SO3] decreases and [SO2] and [O2] increases the equilibrium constant Kc decreases
Presence of a catalyst
• If all other conditions stay the same, the equilibrium constant Kc is not affected by the
presence of a catalyst
• A catalyst speeds up both the forward and reverse reactions at the same rate so the ratio
of [ products ] to [ reactants ] remains unchanged

Worked example: Factors affecting Kc

Answer
Only a change in temperature will affect the value of Kc and any other changes in conditions
would result in the position of the equilibrium moving in such way to oppose this change.
Adding a catalyst will increase the rate of reaction meaning the state of equilibrium will be
reached faster but will have no effect on the position of the equilibrium and therefore Kc is
unchanged.

Worked example: Factors which increase Kp value

Answer
Only temperature changes permanently affect the value of Kp
An increase in temperature shifts the reaction in favour of the products.
The [ products ] increases and [ reactants ] decreases, therefore, the Kp value increases.

Industrial Processes
Haber & Contact Processes
• Equilibrium reactions are involved in some stages of large-scale production of certain
chemicals
• An understanding of equilibrium and Le Chatelier’s principle is therefore very important
in the chemical industry
Haber process
• The Haber process involves the synthesis of ammonia according to:
N2(g) + 3H2(g) ⇌ 2NH3(g) ΔHr = -92 kJ mol-1
• Le Chatelier’s principle is used to get the best yield of ammonia

Maximising the ammonia yield

Pressure
• An increase in pressure will result in the equilibrium shifting in the direction of the
fewest molecules of gas formed to reduce the pressure
 • In this case, the equilibrium shifts towards the right so the yield of ammonia increases
• An increase in pressure will cause the particles to be closer together and therefore
increasing the number of successful collisions leading to an increased reaction rate
• Very high pressures are expensive to produce therefore a compromise pressure of 200
atm is chosen
Temperature
• To get the maximum yield of ammonia the position of equilibrium should be shifted as
far as possible to the right as possible
• Since the Haber process is an exothermic reaction, according to Le Chatelier’s principle
the equilibrium will shift to the right if the temperature is lowered
• A decrease in temperature will decrease the energy of the surroundings so the reaction
will go in the direction in which energy is released to counteract this
• Since the reaction is exothermic, the equilibrium shifts to the right
• However, at a low temperature the gases won’t have enough kinetic energy to collide and
react and therefore equilibrium would not be reached therefore compromise
temperature of 400-450 oC is used in the Haber process
• A heat exchanger warms the incoming gas mixture to give molecules more kinetic
energy such that the gas molecules collide more frequently increasing the likelihood of
a reaction
Removing ammonia
• Removing ammonia by condensing it to a liquid causes the equilibrium position to
shift to the right to replace the ammonia causing more ammonia to be formed from
hydrogen and nitrogen
• The removed ammonia is stored at very low temperatures and there is no catalyst
present with the stored ammonia so the decomposition reaction of ammonia to
decompose back into hydrogen and nitrogen will be too slow
Catalysts
• In the absence of a catalyst the reaction is so slow that hardly anything happens in a
reasonable time!
• Adding an iron catalyst speeds up the rate of reaction
Contact process
• The Contact process involves the synthesis of sulfuric acid according to:
2SO2(g) + O2(g) ⇌ 2SO3(g) ΔHr = -197 kJ mol-1
• Le Chatelier’s principle is used to get the best yield of sulfuric acid

Maximising the sulfuric acid yield

Pressure
• An increase in pressure will result in the equilibrium shifting in the direction of the
fewest molecules of gas formed to reduce the pressure
• In this case, the equilibrium shifts towards the right so the yield of sulfuric acid increases
• In practice, the reaction is carried out at only 1 atm
• This is because Kp for this reaction is already very high meaning that the position of the
equilibrium is already far over to the right
• Higher pressures than 1 atm will be unnecessary and expensive
Temperature
• The same principle applies to increasing the temperature in the Contact process as in the
Haber process
• A compromise temperature of 450 oC is used
Removing sulfuric acid
• SO3 is removed by absorbing it in 98% sulfuric acid
• The SO3 reacts with the solution and more H2SO4 is formed
Catalysts
• The Contact process uses vanadium(V) oxide as a catalyst to increase the rate of reaction

11.2 Brønsted–Lowry Theory Of Acids And Bases

Common Acids
• An acid is a substance that neutralises a base forming a salt and water:
2HCl(aq) + CaO(s) ⇌ CaCl2(aq) + H2O(l)
acid salt

Acids react with bases to form salt and water

• Acids are also substances that release hydrogen ions when they dissolve in water:
HCl(g) → H+(aq) + Cl– (aq)

Acids dissociate in water to release a hydrogen ion

Names & formulae of some common acids table

•In organic acids (such as carboxylic acids) only some of the hydrogen atoms can form
ions when the acid dissociates
Common Alkalis
• A base is a compound that neutralises an acid forming a salt and water
2HCl(aq) + CaO(s) ⇌ CaCl2(aq) + H2O(l)
base salt
 • A base is a substance that accepts hydrogen ions or a compound that contains oxide or
hydroxide ions
For example:
NH3(g) + H2O(l) → NH4+(aq) + OH–(aq)
base hydroxide ions
For example:
NaOH(s) + aq → Na+(aq) + OH–(aq)
base hydroxide ions
• A base that is soluble in water is called an alkali
Names & formulae of some common alkalis table

Brønsted–Lowry Theory
• The Brønsted-Lowry Theory defines acids and bases in terms of proton transfer
between chemical compounds
• A Brønsted-Lowry acid is a species that gives away a proton (H+)
• A Brønsted-Lowry base is a species that accepts a proton (H+) using its lone pair of
electrons

The diagram shows a Brønsted-Lowry acid which donates the proton to the Brønsted-Lowry
base that accepts the proton using its lone pair of electrons

• Species that can act both as acids and bases are called amphoteric
o Eg. water as a Brønsted-Lowry acid
The diagram shows water acting as a Brønsted-Lowry acid by donating a proton to ammonia
which accepts the proton using its lone pair of electrons

The diagram shows a dot & cross diagram for the reaction of water with ammonia to show
how water acts as a Brønsted-Lowry acid and ammonia as a Brønsted-Lowry base

• Eg. water as a Brønsted-Lowry base

The diagram shows water acting as a Brønsted-Lowry base by accepting a proton from
hydrochloric acid proton using its lone pair of electrons
The diagram shows a dot & cross diagram for the reaction of water with hydrochloric acid to
show how water acts as a Brønsted-Lowry base and ammonia as a Brønsted-Lowry acid

• The Brønsted-Lowry Theory is not limited to aqueous solutions only and can also be
applied to reactions that occur in the gas phase

Example of a Brønsted-Lowry acid and base reaction in the gas state

Acid & Base Dissociation

Strong acids
• A strong acid is an acid that dissociates almost completely in aqueous solutions
o HCl (hydrochloric acid), HNO3 (nitric acid) and H2SO4 (sulfuric acid)
• The position of the equilibrium is so far over to the right that you can represent the
reaction as an irreversible reaction

The diagram shows the almost complete dissociation of a strong acid in aqueous solution
 • The solution formed is highly acidic due to the high concentration of the H+/H3O+ ions
• Since the pH depends on the concentration of H+/H3O+ ions, the pH can be calculated if
the concentration of the strong acid is known

pH is the negative log of the concentration of H+/H3O+ ions and can be calculated if the
concentration of the strong acid is known using the stoichiometry of the reaction

Weak acids
• A weak acid is an acid that partially (or incompletely) dissociates in aqueous solutions
o Eg. most organic acids (ethanoic acid), HCN (hydrocyanic acid), H2S (hydrogen
sulfide) and H2CO3 (carbonic acid)
• The position of the equilibrium is more over to the left and an equilibrium is established

The diagram shows the almost complete dissociation of a weak acid in aqueous solution

• The solution is less acidic due to the lower concentration of H+/H3O+ ions
• Finding the pH of a weak acid is a bit more complicated as now the concentration of H+
ions is not equal to the concentration of acid
• To find the concentration of H+ ions, the acid dissociation constant (Ka) should be used
Acid & equilibrium position table
Strong bases
• A strong base is a base that dissociates almost completely in aqueous solutions
E.g. group 1 metal hydroxides such as NaOH (sodium hydroxide)
The position of the equilibrium is so far over to the right that you can represent the
reaction as an irreversible reaction

The diagram shows the almost complete dissociation of a strong base in aqueous solution

• The solution formed is highly basic due to the high concentration of the OH– ions

Weak bases
• A weak base is a base that partially (or incompletely) dissociates in aqueous solutions
o NH3 (ammonia), amines and some hydroxides of transition metals
• The position of the equilibrium is more to the left and an equilibrium is established

The diagram shows the almost complete dissociation of a weak base in aqueous solution

• The solution is less basic due to the lower concentration of OH– ions
Base & equilibrium position table
Exam Tip
Hydrogen ions in aqueous solutions can be written as either as H3O+ or as H+ however, if H3O+ is
used, H2O should be included in the chemical equation:
HCl(g) → H+(aq) + Cl–(aq)
or
HCl(g) + H2O(l) → H3O+(aq) + Cl–(aq)

Remember that some acids are both strong and weak acids – for example, H2SO4 (sulfuric acid)
has two hydrogen ions that can ionise.
H2SO4 acts as a strong acid: H2SO4 → H+ + SO4–
HSO4– acts as a weak acid: HSO4– ⇌ H+ + SO42-

Also, don’t forget that the terms strong and weak acids and bases are related to the degree of
dissociation and not the concentration.
The appropriate terms to use when describing concentration are dilute and concentrated.

The pH Scale
• The pH scale is a numerical scale that shows how acidic or alkaline a solution is
• The values on the pH scale go from 1-14 (extremely acidic substances have values of
below 1)
• All acids have pH values of below 7, all alkalis have pH values above 7
• The lower the pH then the more acidic the solution is
• The higher the pH then the more alkaline the solution is

The pH scale showing acidity, neutrality and alkalinity

pH of water
• An equilibrium exists in water where few water molecules dissociate into proton and
hydroxide ions
H2O(l) ⇌ H+(aq) + OH–(aq)
• The equilibrium constant for this reaction is:

Kc x [H2O] = [H+] [OH–]

• Since the concentration the H+ and OH– ions is very small, the concentration of water is
considered to be a constant, such that the expression can be rewritten as:
Kw = [H+] [OH–]
Where Kw (ionic product of water) = Kc x [H2O]
= 10-14 mol2 dm-3 at 298K
–
• Water at 298K has equal amounts of OH and H+ ions with concentrations of 10-7 mol
dm-3
 • To calculate the pH of water, the following formula should be used:

pH = -log (10-7)
=7
• Thus, water has a pH of 7
pH of acids
• Acidic solutions (strong or weak) always have more H+ than OH– ions
• Since the concentration of H+ is always greater than the concentration of OH– ions, [H+]
is always greater than 10-7 mol dm-3
• Using the pH formula, this means that the pH of acidic solutions is always below 7
• The higher the [H+] of the acid, the lower the pH
pH of bases
• Basic solutions (strong or weak) always have more OH– than H+ ions
• Since the concentration of OH– is always greater than the concentration of H+ ions, [H+]
is always smaller than 10-7 mol dm-3
• Using the pH formula, this means that the pH of basic solutions is always above 7
• The higher the [OH–] of the base, the higher the pH

Strength of Acids & Bases

Strong & Weak Acids & Bases

• Strong and weak acids can be distinguished from each other by their:
o pH value (using a pH meter or universal indicator)
o Electrical conductivity
o Reactivity
pH
• An acid dissociates into H+ in solution according to:
HA → H+ + A–
• The stronger the acid, the greater the concentration of H+ and therefore the lower the
pH
pH value of a strong acid & base table

• The most accurate way to determine the pH is by reading it off a pH meter

• The pH meter is connected to the pH electrode which shows the pH value of the solution
 The diagram shows a digital pH meter that measures the pH of a solution using a pH
electrode
• A less accurate method is to measure the pH using universal indicator paper
• The universal indicator paper is dipped into a solution of acid upon which the paper
changes colour
• The colour is then compared to those on a chart which shows the colours corresponding
to different pH values

The diagram shows the change in colour of the universal indicator paper when dipped in a
strong (HCl) and weak (CH3COOH) acid. The colour chart is used to read off the
corresponding pH values which are between 1-2 for HCl and 3-4 for CH3COOH
Electrical conductivity
• Since a stronger acid has a higher concentration of H+ it conducts electricity better
• Stronger acids therefore have a greater electrical conductivity
• The electrical conductivity can be determined by using a conductivity meter
• Like the pH meter, the conductivity meter is connected to an electrode
• The conductivity of the solution can be read off the meter

The diagram shows a digital conductivity meter that measures the electrical conductivity of a
solution using an electrode
Reactivity
• Strong and weak acids of the same concentrations react differently with reactive metals
• This is because the concentration of H+ is greater in strong acids compared to weak acids
• The greater H+ concentration means that more H2 gas is produced

The diagram shows the reaction of 0.1 mol dm-3 of a strong acid (HCl) with Mg. The reaction
produces a lot of bubbles and hydrogen gas due to the high concentration of H+ present in
solution
 The diagram shows the reaction of 0.1 mol dm-3 of a weak acid (CH3COOH) with Mg. The
reaction produces less bubbles and hydrogen gas due to the lower concentration of H+ present
in solution
Exam Tip
The above-mentioned properties of strong and weak acids depend on their ability to dissociate
and form H+ ions.
Stronger acids dissociate more, producing a greater concentration of H+ ions and therefore
showing lower pH values, greater electrical conductivity and more vigorous reactions with
reactive metals.

Neutralisation Reactions
• A neutralisation reaction is one in which an acid (pH <7) and a base/alkali (pH >7) react
together to form water (pH = 7) and a salt

• The proton of the acid reacts with the hydroxide of the base to form water

• The spectator ions which are not involved in the formation of water, form the salt
 The diagram shows a neutralisation reaction of HCl and NaOH and the two individual
reactions that take place to form the water and salt
• The name of the salt produced can be predicted from the acid that has reacted
Acid reacted & salt table

Exam Tip
Note that the reaction of an acid and metal carbonate also forms carbon dioxide:
acid + metal carbonate → salt + water + carbon dioxide

pH Titration Curves
What are pH titration curves
• Titration is a technique used in neutralisation reactions between acids and alkalis to
determine the concentration of the unknown solution
• It involves adding a titrant of known concentration from a burette into a conical flask
containing the analyte of unknown concentration
• An indicator is added which will change colour at the endpoint of the titration
• The endpoint is the point at which equal number of moles of titrant and analyte react
with each other
• The equivalence point is halfway the vertical region of the curve
Equivalence point → moles of alkali = moles of acid
• This is also known as the equivalence point and this is the point at which neutralisation
takes place

The diagram shows a pH titration curve where the equivalence point is the point at which
equal number of moles of titrant and analyte have reacted
Sketching pH titration curve
• Draw axes with volume added (cm3) on the x-axis and pH on the y-axis

• Draw a horizontal line running parallel to the x-axis at pH 7

o Everything below this line will be in the acidic region and everything above it in
the alkaline region

• Determine which substance is in the conical flask

o If it is a strong acid the initial pH is about 1 or 2
o If it is a weak acid the initial pH is about 3-4
o If it is a strong alkali the initial pH is about 13-14
o If it is a weak alkali the initial pH is about 11
 • Determine what type of acids and alkali are used
o Strong acid + strong alkali
o Strong acid + weak alkali
o Weak acid + strong alkali
o Weak acid + weak alkali

• Draw the pH titration curve

Strong acid + strong alkali pH titration curve

• Initially there are only H+ ions present in solution from the dissociation of the strong acid
(HCl) (initial pH about 1-2)
• As the volume of strong alkali (NaOH) added increases, the pH of the HCl solution
slightly increases too as more and more H+ ions react with the OH– from the NaOH to
form water
• The change in pH is not that much until the volume added gets close to the equivalence
point
• The pH surges upwards very steeply
• The equivalence point is the point at which all H+ ions have been neutralised (therefore
pH is 7 at equivalence point)
• Adding more NaOH will increase the pH as now there is an excess in OH– ions (final pH
about 13-14)
 The diagram shows a pH titration curve of 1.0 mol dm-3 HCl (25 cm3) with NaOH

• The pH titration curve for HCl added to a NaOH has the same shape
• The initial pH and final pH are the other way around
• The equivalence point is still 7

The diagram shows a pH titration curve of 1.0 mol dm-3 NaOH (25 cm3) with HCl

Strong acid + weak alkali pH titration curve

• Initially, there are only H+ ions present in solution from the dissociation of the strong
acid (HCl) (initial pH about 1-2)
• As the volume of weak alkali (NH3) added increases, the pH of the analyte solution
slightly increases too as more and more H+ ions react with the NH3
• The change in pH is not that much until the volume added gets close to the equivalence
point
• The equivalence point is the point at which all H+ ions have been neutralised by the
NH3 however the equivalence point is not neutral, but the solution is still acidic (pH
about 5.5)
• This is because all H+ have reacted with NH3 to form NH4+ which is a relatively strong
acid, causing the solution to be acidic
• As more of the NH3 is added, the pH increases to above 7 but below that of a strong
alkali as NH3 is a weak alkali
 The diagram shows a pH titration curve of 1.0 mol dm-3 HCl (25 cm3) with NH3

• The pH titration curve for strong acid added to a weak alkali has the same shape
• The initial and final pH are the other way around
• The equivalence point is still about 5.5

Weak acid + strong alkali pH titration curve

• Initially there are only H+ ions present in solution from the dissociation of the weak
acid (CH3COOH, ethanoic acid) (initial pH about 3-4)
• As the volume of strong alkali (NaOH) added increases, the pH of the ethanoic acid
solution slightly increases too as more and more H+ ions react with the OH– from the
NaOH to form water
• The change in pH is not that much until the volume added gets close to the equivalence
point
• The pH surges upwards very steeply
• The equivalence point is the point at which all H+ ions have been neutralised by the
OH– ions however the equivalence points is not neutral, but the solution is slightly basic
(pH about 9)
• This is because all H+ in CH3COOH have reacted with OH– however, CH3COO– is a
relatively strong base, causing the solution to be basic
• As more of the NaOH is added, the pH increases to about 13-14

The diagram shows a pH titration curve of 1.0 mol dm-3 HCl (25 cm3) with NH3
 • The pH titration curve for weak acid added to a strong alkali has the same shape
• The initial and final pH are the other way around
• The equivalence point is still about 9

Weak acid + weak alkali pH titration curve

• Initially there are only H+ ions present in solution from the dissociation of the weak acid
(CH3COOH, ethanoic acid) (initial pH about 3-4)
• In these pH titration curves, there is no vertical region
• There is a ‘point of inflexion’ at the equivalence point
• The curve does not provide much other information

The diagram shows a pH titration curve of 1.0 mol dm-3 weak acid (25 cm3) with weak alkali

Indicators used in Titration

Indicators
• Indicators are substances that change colour when they are added to acidic or alkaline
solutions
• When choosing the appropriate indicator, the pH of the equivalence point is very
important
• The two most common indicators that are used in titrations are methyl orange and
phenolphthalein
• Both indicators change colour over a specific pH range

The diagram shows the change in colour from red to yellow of methyl orange over a pH range
of 3.1-4.4 and from colourless to pink of phenolphthalein over a pH range of 8.3-10
Indicator & pH range table

Choosing indicators for titrations

• Strong acid and strong alkali
o The colour change for both indicators takes place at a pH range that falls within
the vertical region of the curve
o Therefore, both indicators can be used

The diagram shows that both indicators can be used to determine the endpoint of the titration
of a strong acid and strong alkali

• Strong acid and weak alkali

o Only methyl orange will change colour at a pH close to the equivalence point
and within the vertical region of the curve

The diagram shows that only methyl orange can be used to determine the endpoint of the
titration of a strong acid and weak alkali
 • Weak acid and strong alkali
o Now, only phenolphthalein will change colour at a pH close to the equivalence
point and within the vertical region of the curve
o The pH range at which methyl orange changes colour falls below the curve

The diagram shows that only phenolphthalein can be used to determine the endpoint of the
titration of a weak acid and strong alkali

• Weak acid and weak alkali

o Neither indicator is useful, and a different method should be considered

The diagram shows that nether indicators can be used to determine the endpoint of the
titration of a weak acid and weak alkali
Summary
• A reversible reaction is one in which the products can be changed back to reactants.
• Chemical equilibrium is dynamic because the backward and forward reactions are both
occurring at the same time.
• A chemical equilibrium is reached when the rates of the forward and reverse reactions
are equal.
• Le Chatelier’s principle states that when the conditions in a chemical equilibrium change,
the position of equilibrium shifts to oppose the change.
• Changes in temperature, pressure and concentration of reactants and products affect the
position of equilibrium.
• For an equilibrium reaction, there is a relationship between the concentrations of the
reactants and products which is given by the equilibrium constant K.
• Equilibrium constants in terms of concentrations, Kc, and partial pressure, Kp, can be
deduced from appropriate data.
• The quantities of reactants and products present at equilibrium can be calculated from the
equilibrium expression and a value of Kc (or Kp), given appropriate data.
• A change in temperature affects the value of the equilibrium constant for a reaction but
changes in concentration, pressure or the presence of a catalyst do not affect the value of
the equilibrium constant.
• The conditions used in the Haber process and the Contact process are chosen so that a
good yield of product is made.
• The Brønsted–Lowry theory of acids and bases states that acids are proton donors and
bases are proton acceptors.
• Strong acids and bases are completely ionised in aqueous solution whereas weak acids
and bases are only slightly ionised.
• Strong and weak acids and bases can be distinguished by the pH values of their aqueous
solutions.
CHAPTER 12
REACTION KINETIC
Learning Objectives:
12. 1 Rate of reaction
12.2 Effect of temperature on reaction rates and the concept of activation energy
12.3 Homogeneous and heterogeneous catalysts

Learning Outcomes:
Candidates should be able to:

→ Explain and use the term rate of reaction, frequency of collisions, effective collisions and non-
effective collisions
→ Explain qualitatively, in terms of frequency of effective collisions, the effect of concentration and
pressure changes on the rate of a reaction
→ Use experimental data to calculate the rate of a reaction
→ Define activation energy, EA, as the minimum energy required for a collision to be effective
→ Sketch and use the Boltzmann distribution to explain the significance of activation energy
→ Explain qualitatively, in terms both of the Boltzmann distribution and of frequency of effective
collisions, the effect of temperature change on the rate of a reaction
→ explain and use the terms catalyst and catalysis
(a) explain that, in the presence of a catalyst, a reaction has a different mechanism, i.e. one of
lower activation energy
(b) explain this catalytic effect in terms of the Boltzmann distribution
(c) construct and interpret a reaction pathway diagram, for a reaction in the presence and
absence of an effective catalyst
 INTRODUCTION:
The Northern Lights (aurora borealis) are the result of many complex reactions taking place in the
upper atmosphere. A knowledge of reaction rates is needed to understand the natural reactions
involved and how these might be disturbed by artificial emissions.

Northern Lights over the Arctic Circle.

12. 1 Rate of reaction

Rate of Reaction: Collision Theory
Reaction rate
• The rate of a reaction is the speed at which a chemical reaction takes place and has units
mol dm-3 s-1
• The rate of a reaction can be calculated by:

Worked example: Calculating the rate of reaction

Answer
• Step 1: Calculate the amount of ethyl ethanoate formed in mol

= 0.0005 mol
• Step 2: Calculate the volume of the reaction mixture in dm3
400 cm3 = 0.400 dm3
• Step 3: Calculate the concentration change of product formed
 = 0.00125 mol dm-3
• Step 4: Calculate the time in seconds
1.0 min = 60.0 s
• Step 5: Use the equation to calculate the rate

= 2.08 x 10-5 mol dm-3 s-1

Collision theory
• The collision theory states that for a chemical reaction to take place the particles need to
collide with each other in the correct orientation and with enough energy
• The minimum energy that colliding particles must have for a collision to be successful
and a reaction to take place is called the activation energy (Ea)
Collision theory table

• An ineffective collision is when particles collide in the wrong orientation or when they
don’t have enough energy and bounce off each other without causing a chemical reaction

(a) shows an ineffective collision due to the particles not having enough energy whereas (b)
shows an effective collision where the particles have the correct orientation and enough
energy for a chemical reaction to take place
Increase in reaction rate
• The collision frequency is the number of collisions per unit time
• When more collision per unit time take place, the number of particles with energy greater
than the Ea increases
• This causes an increase in rate of reaction
• A catalyst is a substance that increases the rate of reaction without taking part in the
chemical reaction by providing the particles an alternative mechanism with a lower
activation energy

Diagram shows that a catalyst increases the rate of a reaction by providing an alternative
pathway which has a lower activation energy

Rate of Reaction: Concentration & Pressure

Concentration
• The more concentrated a solution is, the greater the number of particles in a given
volume of solvent
• An increase in concentration causes in an increased collision frequency and therefore
an increased rate of reaction

The diagram shows a higher concentration of particles in (b) which means that there are more
particles present in the same volume than (a) so the chances and frequency of collisions
between reacting particles is increased causing an increased rate of reaction

Pressure
• An increase in pressure in reactions that involve gases has the same effect as an increased
concentration of solutions
• When the pressure is increased, the molecules have less space in which they can move
• This means that the number of effective collisions increases due to an increased collision
frequency
 • An increase in pressure therefore increases the rate of reaction

The diagram shows a higher pressure in (b) which means that the same number of particles
occupy a smaller volume, resulting in an increased collision frequency and therefore
increased rate of reaction

Rate of Reaction: Experimental Calculations

• During a reaction, the reactants are used up and changed into the products
• This means that as the reaction proceeds, the concentration of the reactants is decreasing
and the concentration of the products is increasing
• Because of this, the rate of the reaction is not the same throughout the reaction but
changes
• The rate of reaction during the reaction can be calculated from a concentration-time
graph.
• The isomerisation of cyclopropane to propene will be taken as an example:

Isomerisation of cyclopropane
• The concentrations of reactant (cyclopropane) and product (propene) over time can be
experimentally obtained
Concentrations of cyclopropane & propene table
 • When taking the measurements, the temperature should be kept the same at all times as
a change in temperature will change the rate of reaction
• A concentration-time graph for the concentration of propene as well as cyclopropane
can be obtained from the above results
o As an example, the concentration-time graph for propene is shown below:

The graph shows that the concentration of propene increases with time
Calculating the rate at the start of a reaction
• At the start of the reaction, the concentration-time curve looks almost linear
• The rate at this point can therefore be found by treating the curve as a linear line and by
using:

• Using the graph, the average rate of the reaction over the first 5 minutes for propene is:

Line a shows the average rate over the first five minutes whereas line b shows the actual initial
rate found by drawing a tangent at the start of the curve. The calculated rates are very similar
for both methods

= 0.0009 mol dm-3 s-1

Calculating the rate as the reaction proceeds
• The curve becomes shallower with time which means that the rate decreases with time
• The rate of reaction can be calculated by taking short time intervals
Eg. you can calculate the rate of reaction from 15 to 20 mins during which the
concentration of propene increases from 0.68 to 0.83 mol dm-3:

= 0.0005 mol dm-3 s-1

• The smaller the time intervals, the more accurate the reaction rate value is
• Even more accurate is to find the rate of reaction at different concentrations of reactant
or product at particular time points
• This can be done by drawing tangents at several points on the graph
o As an example, the rates of reaction at different concentrations of cyclopropane
are calculated by drawing the appropriate tangents:

The rate of reaction at 3 different concentrations of cyclopropane is calculated by drawing

tangents at those points in the graph

Rate-concentration graph
• The calculated rates can then be summarised in a table to show how the rate of reaction
changes with changing concentration of the reactants or products
Change in rate with decreasing concentration of cyclopropane table
• This data can then be used to plot a rate-concentration graph
• The graph shows that the rate is directly proportional to the concentration of
cyclopropane
o If you double the concentration of cyclopropane the rate of reaction will double
too

The graph shows a directly proportional correlation between the concentration of

cyclopropane and the rate of reaction
12.2 Effect of temperature on reaction rates and the concept of activation
energy
Activation Energy
• For a reaction to take place, the reactant particles need to overcome a minimum amount
of energy
• This energy is called the activation energy (Ea)
• In exothermic reactions the reactants are higher in energy than the products
• In endothermic reactions the reactants are lower in energy than the products
• Therefore, the Ea in endothermic reactions in endothermic reactions is relatively larger
than in exothermic reaction

The diagram shows that the reactants are higher in energy than the products in the
exothermic reaction, so the energy needed for the reactants to go over the energy barrier is
relatively small

The diagram shows that the reactants are lower in energy than the products in the
endothermic reaction, so the energy needed for the reactants to go over the energy barrier is
relatively large
 • Even though particles collide with each other in the same orientation, if they don’t
possess a minimum energy that corresponds to the Ea of that reaction, the reaction will
not take place
• Therefore, for a collision to be effective the reactant particles must collide in the correct
orientation AND possess a minimum energy equal to the Ea of that reaction

Exam Tip
The activation energy is the energy needed to ‘activate’ the reactant particles in order for them to
collide effectively and cause a chemical reaction.

Boltzmann Distribution Curves

Boltzmann distribution curve
• The Boltzmann distribution curve is a graph that shows the distribution of energies at a
certain temperature
• In a sample of a substance, a few particles will have very low energy, a few particles will
have very high energy, and many particles will have energy in between

The Boltzmann distribution curve shows the distribution of the energies and the activation
energy

• The graph shows that only a small proportion of molecules in the sample have enough
energy for an effective collision and for a chemical reaction to take place

Changes in temperature
• When the temperature of a reaction mixture is increased, the particles gain more kinetic
energy
• This causes the particles to move around faster resulting in more frequent collisions
• Furthermore, the proportion of successful collisions increases, meaning a higher
proportion of the particles possess the minimum amount of energy (activation energy) to
cause a chemical reaction
• With higher temperatures, the Boltzmann distribution curve flattens and the peak shifts
to the right
 The Boltzmann distribution curve at T oC and when the temperature is increased by 10 oC
• Therefore, an increase in temperature causes an increased rate of reaction due to:
o There being more effective collisions as the particles have more kinetic energy,
making them move around faster
o A greater proportion of the molecules having kinetic energy greater than the
activation energy

12.3 Homogeneous and heterogeneous catalysts

Catalysts
• Catalysis is the process in which the rate of a chemical reaction is increased, by adding a
substance called a catalyst
• A catalyst increases the rate of a reaction by providing the reactants with an alternative
reaction pathway which is lower in activation energy than the uncatalysed reaction
• Catalysts can be divided into two types:
o Homogeneous catalysts
o Heterogeneous catalysts
• Homogeneous means that the catalyst is in the same phase as the reactants
o For example, the reactants and the catalysts are all liquids
• Heterogeneous means that the catalyst is in a different phase to the reactants
o For example, the reactants are gases but the catalyst used is a solid

The diagram shows that the catalyst speeds up a reaction that would normally be slow due to
the high activation energy. The catalyst is not used up in the chemical reaction and is not
taking part in the chemical reaction
 The diagram shows that the catalyst allows the reaction to take place through a different
mechanism, which has a lower activation energy than the original reaction

Boltzmann distribution curve

• Catalyst provide the reactants another pathway which has a lower activation energy
• By lowering Ea, a greater proportion of molecules in the reaction mixture have
sufficient energy for an effective collision
• As a result of this, the rate of the catalysed reaction is increased compared to the
uncatalyzed reaction

The diagram shows that the total shaded area (both dark and light shading) under the curve
shows the number of particles with energy greater than the Ea when a catalyst is present.
This area is much larger than the dark shaded area which shows the number of particles
with energy greater than the Ea without a catalyst
Summary
• Rate of reaction is a measure of the rate at which reactants are used up or the rate at
which products are formed. The units of rate are mol dm⁻³s⁻¹.
• Rate of reaction is related to concentrations of reactants by a rate equation, which can
only be determined by experiment.
• The general form of the rate equation is: rate = k[A]m[B]n, where:
– k is the rate constant
– [A] and [B] are the concentrations of those reactants that affect the rate of reaction
– m is the order of the reaction with respect to A and n is the order of reaction with
respect to B.
• The overall order of reaction is the sum of the orders in the rate equation. For the
previous example: overall order is m + n
• The order of reaction for a given reactant can be determined experimentally by either:
– measuring the initial rate of reaction using different concentrations of a given reactant
while keeping the concentrations of all other reactants fixed, or
– determining the change in concentration of a specific reactant as the experiment
proceeds, the rate being calculated from tangents taken at several points on the graph.
• The order of reaction can be determined from graphs of reaction rate against
concentration.
• The half-life of a reaction is the time taken for the concentration of a reactant to halve.
• In a first-order reaction the half-life is independent of the concentration(s) of the
reactant(s).
• The rate-determining step is the slowest step in a reaction mechanism. The rate-
determining step determines the overall rate of reaction.
• The order of reaction with respect to a particular reactant shows how many molecules
of that reactant are involved in the rate-determining step of a reaction.
• The rate equation provides evidence to support the suggestion of a reaction mechanism.
• The order of a reaction can be predicted from a given reaction mechanism knowing the
rate-limiting step.
• Homogeneous catalysis occurs when a catalyst and the reactants are in the same phase.
• The mechanism of homogeneous catalysis usually involves redox reactions.
• Examples of homogeneous catalysis include:
– the catalytic role of atmospheric oxides of nitrogen in the atmospheric oxidation of
sulfur dioxide
– Fe²⁺ or Fe³⁺ ions catalysing the reaction between iodide ions and peroxodisulfate ions.
• Heterogeneous catalysis occurs when a catalyst is in a different phase from the
reactants.
• The mechanism of heterogeneous catalysis involves the processes of adsorption,
reaction and desorption.
• Examples of heterogeneous catalysis include:
– the use of iron in the Haber process
– the catalytic removal of oxides of nitrogen in the exhaust gases from car engines.
 ORGANIC CHEMISTRY
1. AN INTRODUCTION TO ORGANIC CHEMISTRY

Learning outcomes
Candidates should be able to:
1. Define the term hydrocarbon as a compound made up of C and H atoms only
2. Understand that alkanes are simple hydrocarbons with no functional group
3. Understand that the compounds in the table contain a functional group which dictates
their physical and chemical properties
4. Interpret and use the general, structural, displayed and skeletal formulae of the classes of
compound stated in the table
5. Understand and use systematic nomenclature of simple aliphatic organic molecules with
functional groups detailed in the table, up to six carbon atoms (six plus six for esters,
straight chains only for esters and nitriles)
6. Deduce the molecular and/or empirical formula of a compound, given its structural,
displayed or skeletal formula

A. Formulae, Functional Groups & the Naming of Organic Compounds

B. Characteristic organic reactions
Learning outcomes
Candidates should be able to:
1. Interpret and use the following terminology associated with types of organic compounds
and reactions:
(a) homologous series
(b) saturated and unsaturated
(c) homolytic and heterolytic fission
(d) free radical, initiation, propagation, termination (the use of arrows to show movement of
single electrons is not required)
(e) nucleophile, electrophile, nucleophilic, electrophilic
(f) addition, substitution, elimination, hydrolysis, condensation
(g) oxidation and reduction
(in equations for organic redox reactions, the symbol [O] can be used to represent one atom
of oxygen from an oxidising agent and the symbol [H] one atom of hydrogen from a reducing
agent)
2. Understand and use the following terminology associated with types of organic
mechanisms:
(a) free-radical substitution
(b) electrophilic addition
(c) nucleophilic substitution
(d) nucleophilic addition
(in organic reaction mechanisms, the use of curly arrows to represent movement of electron
pairs is expected; the arrow should begin at a bond or a lone pair of electrons)
C. Shapes of organic molecules; σ and π bonds

Learning outcomes
Candidates should be able to:
1. Describe organic molecules as either straight-chained, branched or cyclic
2. Describe and explain the shape of, and bond angles in, molecules containing sp, sp2 and
sp3 hybridised atoms
3. Describe the arrangement of σ and π bonds in molecules containing sp, sp2 and sp3
hybridised atoms
4. Understand and use the term planar when describing the arrangement of atoms in organic
molecules, for example ethane
D. Isomerism: structural and stereoisomerism

Learning outcomes
Candidates should be able to:
1. Describe structural isomerism and its division into chain, positional and functional group
isomerism
2. Describe stereoisomerism and its division into geometrical (cis/trans) and optical
isomerism (use of E, Z nomenclature is acceptable but is not required)
3. Describe geometrical (cis/trans) isomerism in alkenes, and explain its origin in terms of
restricted rotation due to the presence of π bonds
4. Explain what is meant by a chiral centre and that such a centre gives rise to two optical
isomers (enantiomers)
(Candidates should appreciate that compounds can contain more than one chiral centre,
but knowledge of meso compounds, or nomenclature such as diastereoisomers is not
required)
5. Identify chiral centres and geometrical (cis/trans) isomerism in a molecule of given
structural formula including cyclic compounds
6. Deduce the possible isomers for an organic molecule of known molecular formula
SELF ASSESSMENT QUESTIONS :
2. HYDROCARBONS

A. ALKANES

Learning outcomes
Candidates should be able to:
1. Recall the reactions (reagents and conditions) by which alkanes can be produced:
(a) addition of hydrogen to an alkene in a hydrogenation reaction, H (g) and Pt/Ni catalyst
2

and heat
(b) cracking of a longer chain alkane, heat with Al O 2 3

2. Describe:
(a) the complete and incomplete combustion of alkanes
(b) the free-radical substitution of alkanes by Cl or Br in the presence of ultraviolet light,
2 2

as exemplified by the reactions of ethane

3. Describe the mechanism of free-radical substitution with reference to the initiation,
propagation and termination steps
4. Suggest how cracking can be used to obtain more useful alkanes and alkenes of lower Mr
from heavier crude oil fractions
5. Understand the general unreactivity of alkanes, including towards polar reagents in terms
of the strength of the C–H bonds and their relative lack of polarity
6. Recognise the environmental consequences of carbon monoxide, oxides of nitrogen and
unburnt hydrocarbons arising from the combustion of alkanes in the internal combustion
engine and of their catalytic removal
B. ALKENES

Learning outcomes
Candidates should be able to:
1. Recall the reactions (including reagents and conditions) by which alkenes can be
produced:
(a) elimination of HX from a halogenoalkane by ethanolic NaOH and heat
(b) dehydration of an alcohol, by using a heated catalyst (e.g. Al O ) or a concentrated acid
2 3

(c) cracking of a longer chain alkane

2. Describe the following reactions of alkenes:

(a) the electrophilic addition of
(i) hydrogen in a hydrogenation reaction, H (g) and Pt/Ni catalyst and heat
2

(ii) steam, H O(g) and H PO catalyst

2 3 4

(iii) a hydrogen halide, HX(g) at room temperature

(iv) a halogen, X
2
 (b) the oxidation by cold dilute acidified KMnO to form the diol
4

(c) the oxidation by hot concentrated acidified KMnO leading to the rupture of the
4

carbon–carbon double bond and the identities of the subsequent products to determine
the position of alkene linkages in larger molecules
(d) addition polymerisation exemplified by the reactions of ethene and propene
3. Describe the use of aqueous bromine to show the presence of a C=C bond
4. Describe the mechanism of electrophilic addition in alkenes, using bromine / ethene and
hydrogen bromide / propene as examples
5. Describe and explain the inductive effects of alkyl groups on the stability of primary,
secondary and tertiary cations formed during electrophilic addition (this should be used to
explain Markovnikov addition)
SELF ASSESSMENT QUESTIONS
3. HALOGEN DERIVATIVES

Learning outcomes
Candidates should be able to:
1. Recall the reactions (reagents and conditions) by which halogenoalkanes can be produced:
(a) the free-radical substitution of alkanes by Cl2 or Br2 in the presence of ultraviolet light,
as exemplified by the reactions of ethane
(b) electrophilic addition of an alkene with a halogen, X2, or hydrogen halide, HX(g), at
room temperature
(c) substitution of an alcohol, e.g. by reaction with HX or KBr with H2SO4 or H3PO4; or
with PCl3 and heat; or with PCl5; or with SOCl2
2. Classify halogenoalkanes into primary, secondary and tertiary
3. Describe the following nucleophilic substitution reactions:
(a) the reaction with NaOH(aq) and heat to produce an alcohol
(b) the reaction with KCN in ethanol and heat to produce a nitrile
(c) the reaction with NH3 in ethanol heated under pressure to produce an amine
(d) the reaction with aqueous silver nitrate in ethanol as a method of identifying the
halogen present as exemplified by bromoethane
4. Describe the elimination reaction with NaOH in ethanol and heat to produce an alkene as
exemplified by bromoethane
5. Describe the SN1 and SN2 mechanisms of nucleophilic substitution in halogenoalkanes
including the inductive effects of alkyl groups
6. Recall that primary halogenoalkanes tend to react via the SN2 mechanism; tertiary
halogenoalkanes via the SN1 mechanism; and secondary halogenoalkanes by a mixture of
the two, depending on structure
7. Describe and explain the different reactivities of halogenoalkanes (with particular
reference to the relative strengths of the C–X bonds as exemplified by the reactions of
halogenoalkanes with aqueous silver nitrates)
SELF ASSESSMENT QUESTIONS
4. HYDROXY COMPOUNDS

Learning outcomes
Candidates should be able to:
1. Recall the reactions (reagents and conditions) by which alcohols can be produced:
(a) electrophilic addition of steam to an alkene, H2O(g) and H3PO4 catalyst
(b) reaction of alkenes with cold dilute acidified potassium manganate(VII) to form a diol
(c) substitution of a halogenoalkane using NaOH(aq) and heat
(d) reduction of an aldehyde or ketone using NaBH4 or LiAl H4
(e) reduction of a carboxylic acid using LiAl H4
(f) hydrolysis of an ester using dilute acid or dilute alkali and heat
2. Describe:
(a) the reaction with oxygen (combustion)
(b) substitution to halogenoalkanes, e.g. by reaction with HX or KBr with H2SO4 or H3PO4;
or with PCl3 and heat; or with PCl5; or with SOCl2
(c) the reaction with Na(s)
(d) oxidation with acidified K2Cr2O7 or acidified KMnO4 to:
(i) carbonyl compounds by distillation
(ii) carboxylic acids by refluxing
(primary alcohols give aldehydes which can be further oxidised to carboxylic acids,
secondary alcohols give ketones, tertiary alcohols cannot be oxidised)
(e) dehydration to an alkene, by using a heated catalyst, e.g. Al2O3 or a concentrated acid
(f) formation of esters by reaction with carboxylic acids and concentrated H2SO4 or H3PO4
as catalyst as exemplified by ethanol
3 (a) classify alcohols as primary, secondary and tertiary alcohols, to include examples with
more than one alcohol group
(b) state characteristic distinguishing reactions, e.g. mild oxidation with acidified K2Cr2O7,
 colour change from orange to green
4. Deduce the presence of a CH3CH(OH)– group in an alcohol, CH3CH(OH)–R, from its
reaction with alkaline I2(aq) to form a yellow precipitate of tri-iodomethane and an ion,
RCO2–
5. Explain the acidity of alcohols compared with water
SELF ASSESSMENT QUESTIONS
5. CARBONYL COMPOUNDS

Learning outcomes
Candidates should be able to:
1. Recall the reactions (reagents and conditions) by which aldehydes and ketones can be
produced:
(a) the oxidation of primary alcohols using acidified K Cr O or acidified KMnO and
2 2 7 4

distillation to produce aldehydes

(b) the oxidation of secondary alcohols using acidified K Cr O or acidified KMnO and
2 2 7 4

distillation to produce ketones

2. Describe:
(a) the reduction of aldehydes and ketones, using NaBH or LiAl H to produce alcohols
4 4

(b) the reaction of aldehydes and ketones with HCN, KCN as catalyst, and heat to
produce hydroxynitriles exemplified by ethanal and propanone
3. Describe the mechanism of the nucleophilic addition reactions of hydrogen cyanide with
aldehydes and ketones
4. Describe the use of 2,4-dinitrophenylhydrazine (2,4-DNPH reagent) to detect the presence
of carbonyl compounds
5. Deduce the nature (aldehyde or ketone) of an unknown carbonyl compound from the
results of simple tests (Fehling’s and Tollens’ reagents; ease of oxidation)
6. Deduce the presence of a CH3CO – group in an aldehyde or ketone, CH3CO–R, from its
reaction with alkaline I2(aq) to form a yellow precipitate of tri-iodomethane and an ion,
RCO2–
SELF ASSESSMENT QUESTIONS
6. CARBOXYLIC ACIDS AND DERIVATIVES

Learning outcomes
Candidates should be able to:
1. Recall the reactions by which carboxylic acids can be produced:
(a) oxidation of primary alcohols and aldehydes with acidified K Cr O or acidified
2 2 7

KMnO and refluxing

4

(b) hydrolysis of nitriles with dilute acid or dilute alkali followed by acidification
(c) hydrolysis of esters with dilute acid or dilute alkali and heat followed by acidification
2. Describe:
(a) the redox reaction with reactive metals to produce a salt and H2(g)
(b) the neutralisation reaction with alkalis to produce a salt and H O(l )
2
(c) the acid–base reaction with carbonates to produce a salt and H O(l) and CO (g)
2 2

(d) esterification with alcohols with concentrated H SO as catalyst

2 4

(e) reduction by LiAl H to form a primary alcohol

4
SELF ASSESSMENTS QUESTIONS
7. ANALYTICAL TECHNIQUES

Learning outcomes
Candidates should be able to:
1. Analyse an infrared spectrum of a simple molecule to identify functional groups (see the
Data section for the functional groups required)
SELF ASSESSMENT QUESTIONS