CHAPTER 1

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 surrounding a very small, dense nucleus that
contains protons and neutrons
● The nucleus has an overall positive charge due to the presence of these protons
● Negatively charged electrons are found in shells in the empty space around the nucleus

Subatomic Particles

● Subatomic particles are the particles an element is made up of and

include protons, neutrons and electrons
● These subatomic particles are so small that it is not possible to measure their masses
and charges using conventional units (such as grams and coulombs)
● Instead, their masses and charges are compared to each other
using ‘relative atomic masses’ and ‘relative atomic charges’
● These are not actual charges and masses but they are charges and masses of particles
relative to each other
o Protons and neutrons have a very similar mass so each is assigned a relative
mass of 1 whereas electrons are 1836 times smaller than a proton and neutron
o Protons are positively charged, electrons negatively charged and neutrons
are neutral
● The relative mass and charge of the subatomic particles are:

Relative mass & charge of subatomic particles table

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 coulombs, however, relative to each other, their charges are -1 and +1
respectively.

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CHAPTER 1

Atoms: Key Terms

● The atomic number (or proton number) is the number of protons in the nucleus of an
atom and has symbol Z
o The atomic number is equal to the number of electrons present in a neutral atom
of an element
o Eg. the atomic number of lithium is 3 which suggests that the neutral lithium atom
has 3 protons and 3 electrons
● The mass number (or nucleon number) is the total number of protons and neutrons in
the nucleus of an atom and has symbol A
● The number of neutrons can be calculated by:

Number of neutrons = mass number – atomic number

●
o Protons and neutrons are also called nucleons

The mass (nucleon) and atomic (proton) number are given for each element in the Periodic
Table

Mass & Charge Distribution

● The mass of an atom is concentrated in the nucleus as 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 holds an atom together

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CHAPTER 1

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 suggests that the electron is negatively charged as 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 towards the negative plate
o This suggests that the proton is positively charged
o As protons are deflected less than electrons, this shows that protons
are heavier than electrons
● A beam of neutrons is not deflected at all
o Which suggests that the particle is neutral in character as it is not attracted to
either the negative or positive plate

Determining the Subatomic Structure of Atoms & Ions

3
CHAPTER 1

● An atom is neutral and has no overall charge

● Ions on the other hand have either gained or lost 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 Eg. 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

Worked example: Determine the number of protons

4
CHAPTER 1

Electrons

● An atom is neutral and therefore has the same number of protons and electrons
● 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

Worked example: Determine the number of 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)

5
CHAPTER 1

Worked example: Determine the number of neutrons

Nu
mber of neutrons = mass number (A) – number of protons (Z)

Number of neutrons = 63 – 29

Number of neutrons = 34

●
o The neutral atom of element X has 34 neutrons in its nucleus

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

6
CHAPTER 1

● 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 radii 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

7
CHAPTER 1

● 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

8
CHAPTER 1

Isotopes: Basics

● Isotopes are atoms of the same element that contain the same number of protons and
electrons but a different number of neutrons
● The symbol for an isotope is the chemical symbol (or word) followed by a dash and
then the mass number
o Eg. carbon-12 and carbon-14 are isotopes of carbon containing 6 and 8 neutrons
respectively

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

Electron Shells: Basics

Shells

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

9
CHAPTER 1

● 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

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:

10
CHAPTER 1

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

● The 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
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 3D shapes

11
CHAPTER 1

● 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

12
CHAPTER 1

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

13
CHAPTER 1

Summary of the arrangement of electrons in atoms table

Subshells & Energy

● The principal quantum shells increase in energy with increasing principal quantum
number
o Eg. 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, so the 3d orbital is filled before the 4s orbital
● All the orbitals in the same subshell have the same energy and are said to be degenerate
o Eg. px, py and pz are all equal in energy

The s & p Orbitals

14
CHAPTER 1

s orbitals

● The s orbitals are spherical in shape

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

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

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

15
CHAPTER 1

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 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

16
CHAPTER 1

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 bottom to top
● 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

17
CHAPTER 1

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 1s 22s22p63s23p5
o Two of the three p orbitals have paired electrons whereas one of them has an
unpaired electron

Free radicals are formed when a molecule undergoes homolytic fission where the two electrons
of a covalent bond are split evenly between the two atoms.

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

18
CHAPTER 1

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 (valence electron(s) in s orbital)
o p block elements (valence electron(s) in p orbital)
o d block elements (valence electron(s) in d orbital)
o f block elements (valence electron(s) in f orbital)

Exceptions

● Chromium and copper have the following electron configurations:

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

19
CHAPTER 1

Worked example: Electron configuration

The shorthand versi

2
on is [Ar] 4s since argon is the nearest preceding noble gas to calcium which accounts for 18
electrons

Answer 3: Gallium has 31 electrons so the full electronic configuration is:

[Ar] 3d10 4s2 4p1

Answer 4: What this means is that if you ionise calcium and remove two of its outer electrons,
the electronic configuration of the Ca2+ ion is identical to that of argon

Ca2+ is 1s2 2s2 2p6 3s2 3p6

Ar is also 1s2 2s2 2p6 3s2 3p6

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 atoms of an element in the gaseous
state 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 the first electron
from an atom of an element
o Eg. the first ionisation energy of gaseous calcium:

+
Ca(g) Ca (g) + e– IE1 = 590 kJ mol-1

20
CHAPTER 1

Ionisation Energies: Equations

● The second ionisation energy (IE2) is the energy required to remove the second
electron from each ion in a mole of gaseous +1 ions
● The third ionisation energy (IE3) is the energy required to remove the third electron
from each ion in a mole of gaseous +2 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

Remember that equations to represent ionisation energies must have gaseous (g) state symbols
for the atoms and ions but not for the electrons.

Ionisation Energies: Trends

● Ionisation energies show periodicity

● As could be expected from their electronic configuration, the group I metals show low IE
whereas the noble gases have very high IE’s
● The first ionisation energy increases across a period and decreases down a group caused
by four factors that influence the ionisation energy
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 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 to feel the full
nuclear charge so the greater the shielding of outer electrons by inner electron
shells, the lower the ionisation energy

21
CHAPTER 1

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)

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 The distance between the nucleus and outer electron remains
reasonably constant
o The shielding by inner shell electrons remain reasonably constant
● There is a rapid decrease in ionisation energy between the last element in one period and
the first element in the next period caused by:
o The increased distance between the nucleus and the outer electrons
o The increased shielding by inner electrons
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

22
CHAPTER 1

Ionisation energy down a group

● The ionisation energy down a group decreases due to the following factors:
o Across a period the nuclear charge increases
o The distance between the nucleus and outer electron increases
o The shielding by inner shell electrons increases

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 as 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

23
CHAPTER 1

● 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 less difficult as the orbital is no longer full and there is
less spin-pair repulsion
● It is easy to remove electrons from a full subshell as they undergo spin-pair repulsion.
● It gets more difficult to remove electrons from principal quantum shells that get closer
to the nucleus as there is less shielding and an increase in attractive forces between the
electrons and nuclear charge.

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:

24
CHAPTER 1

● 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

● 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

25
CHAPTER 1

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

26
CHAPTER 1

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

Find the large jumps by subtracting the successive ionisation energies from each other to
identify when an electron has been removed from a different subshell.

27