CHAPTER 2

ELECTRONS
IN ATOMS
 Learning outcomes
Here’s what you’ll find in this chapter:
● Undestand that electrons in an atom can only exist in certain energy levels (shells) outside the nucleus
● Use and understand the term shells, sub-shells, orbitals, principal quantum number (n), ground state, electronic
configuration
● Describe the number of orbitals making up s,p, and d sub-shells and the number of electrons that can fill the
sub-shells
● Describe the order of increasig energy of the sub-shells within the first 3 shells and the 4s and 4p sub-shells
● Describe the electronic configuration in each shells, sub-shell and orbital
● Exlain the electronic configuration in term of the energy of electrons and inter-electron repulsion
● Determine the electronic configuration given the atomic (proton) number and charge using either full or
shorthand electronic configuration
● Use and understand the ‘electrons in boxes’ notation
● Describe and sketch the shape of s and p orbital
● Describe a free radical as a species with one or more unpaired electrons
● Define the term first ionisation energy
● Construst equation to represent first, second and subsequent ionisation energies
● Identify and explain the trend in ionisation energies across a period and down a group of the periodic table
 Learning outcomes
continue
● Identify and explain the variation in successive ionisation energy of an element
● Describe and understand that ionisation energies are due to the attraction between the nucleus and the outer
electron
● Explain the factor influencing the ionisation energy of the element ( in term 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
● Explain qualitatively the variations in atomic radius & ionic radius across a period and down the group.
 Table of Contents

2.1 2.2 2.3 2.4

Simple Evidence for Sub-shells &
electronic Electronic
electronic atomic
structure configuration
structure orbitals

2.5 2.6
Periodic patterns Patterns in
of atomic & ionic ionisations energies
radii in periodic table
 2.1 Simple electronic structure
• 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

• The lower the principal quantum number, the closer the shell is to the
nucleus

• The higher the principal quantum number, have more energy and are
held less tightly to the nucleus
 Key definition
• Energy levels:
Each electron in an atom has its
particular average amount of energy.
• Each principal quantum number The further away the electron is from
has a fixed number of electrons the nucleus, the more energy it has.
it can hold Each principal energy level (symbol n)
corresponds to an electron shell at a
n = 1 : up to 2 electrons certain distance from the nucleus.
n = 2 : up to 8 electrons Energy levels are split up into sub-levels
n = 3 : up to 18 electrons which are given the names s,p,d, etc.
n = 4 : up to 32 electrons
• Electronic configuration:
A way of representing the arrangement
of the electrons in atoms showing the
principal quantum shells, the sub-
shells, and the number of electrons
present, eg. 1s2 2s2 2p3. The electrons
may also be shown in boxes.
 Atomic Number of
no. electrons in shell

Simple electronic configuration of the first 11 elements in

n=1 n=2 n=3

H 1 1

He 2 2

Li 3 2 1

Be 4 2 2

B 5 2 3

C 6 2 4
Lithium Neon Chlorine N 7 2 5
2,1 2,8 2,8,7

the periodic table

O 8 2 6
The simple electronic structure of lithium, neon, and chlorine.
F 9 2 7
The nuclei of the atom are not shown.
Ne 10 2 8

Na 11 2 8 1
 Question
● Write the simple electronic
configurations of the following atoms,
showing the principal quantum shells
only:

● a) sulfur, Z=16
● b) magnesium, Z=12
● c) fluorine, Z= 9
● d) potassium, Z=19
● e) carbon, Z= 6
 2.2 Evidence for electronic
structure Key definition

Ionisation energy First ionisation

• By firing high-speed electrons at atom, scientist can work energy, IE1:
out how much energy has to be supplied to form an ion
by knocking out one electron from each other The energy
• That energy is called the ionisation energy needed to
remove 1 mole of
• Ionisation energies are measured under standard electrons from 1
conditions which are 298 K and 1 atm mole of atoms of
• The units of IE are kilojoules per mole (kJ mol-1) an element in the
gaseous state to
E.g. the first ionisation energy of gaseous calcium: form 1 mole of
gaseous ions.
Ca(g) → Ca+ (g) + e– IE1 = +590 kJ mol-1
● 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 Key definition

Ca+ (g) → Ca2+ (g) + e- IE2 =1150 kJ mol-1 successive

ionisation
● The third ionisation energy (IE3) is the energy required energy:
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 energy
required in each
Ca2+ (g) → Ca3+ (g) + e- IE3 = 4940 kJ mol-1 step to remove
the first electron,
● And so on… then the second,
then the third,
● The electrons from an atom can be continued to be and so on, from a
removed until only the nucleus is left gaseous atom.

● This sequence of ionisation energies is called successive

ionisation energies
 More ionisation energies
● You can then have as many successive ionisation energies as there are
electrons in the original atom.

● The first four ionisation energies of aluminium, for example, are given by

● 1st I.E. = 577 kJ mol-1

● 2nd I.E. = 1820 kJ mol-1
● 3rd I.E. = 2740 kJ mol-1
● 4th I.E. = 11600 kJ mol-1
● In order to form an Al3+ (g) ion from Al (g) you would have to supply:

● 577 + 1820 + 2740 = 5137 kJ mol-1

● That's a lot of energy. Why, then, does aluminium form Al 3+ ions?

● It can only form them if it can get that energy back from somewhere,
and whether that's feasible depends on what it is reacting with.

● For example, if aluminium reacts with fluorine or oxygen, it can

recover that energy in various changes involving the fluorine or
oxygen - and so aluminium fluoride or aluminium oxide contain Al 3+
ions.

● If it reacts with chlorine, it can't recover sufficient energy, and so solid

anhydrous aluminium chloride isn't actually ionic - instead, it forms
covalent bonds.

● Why doesn't aluminium form an Al4+ ion? The fourth ionisation energy
is huge compared with the first three, and there is nothing that
aluminium can react with which would enable it to recover that
amount of extra energy.
 WHY???
● Make sure to include the state symbol each time. WHY???

● [because it is part of the definition for ionisation energy above]

● The ionisation energy is an exothermic or endothermic process.

WHY???

● [It is endothermic because energy is needed to remove electrons.]

● energy input is required for ionisation of atom. WHY???

● [it is needed because the negative outer electron is attracted by the

positive nucleus.]
Successive ionisation energies of elements
 why successive ionisations display a general
increase.??
● Because the net positive charge on the ion gets greater as
each electron is removed.

● As each electron is removed, there is a greater attractive

force between the proton ( in the nucleus) and the
remaining electrons.

● Therefore more energy is needed to overcome this forces

 QUESTION
a) write equations that describe:

i the 1st ionisation energy of calcium

ii the 3rd ionisation energy of potassium
iii the 2nd ionisation energy of lithium
iv the 5th ionisation energy of sulfur

b) The 2nd ionisation energy of nitrogen is 2860 kJ mol -1. Explain why the
3rd ionisation energy is higher.
The following activity ‘Ionisation energy – true or false?’
provides 20 questions to help learners focus on some of the
common misconceptions on ionisation energies:

https://edu.rsc.org/download?ac=13336
 Factors that influence ionisation energy
• 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:

1 Size of the nuclear charge

The nuclear charge increases

2 Distance of outer electrons from
the nucleus

with increasing atomic number, Electrons in shells that are further

which means that there are away from the nucleus are less
greater attractive forces betwee attracted to the nucleus – the nuclear
n the nucleus and electrons, so attraction is weaker – so the further
more energy is required to the outer electron shell is from the
overcome these attractive forces nucleus, the lower the ionisation
when removing an electron energy
 4
Shielding effect of inner electrons Spin-pair repulsion

3 The shielding effect is when the

electrons in full inner shells repel
Electrons in the same atomic orbital
in a subshell repel each other more
electrons in outer shells, preventing them than electrons in different atomic
from feeling the full nuclear charge, so orbitals which makes it easier to
the more shells an atom has, the greater remove an electron (which is why
the shielding effect, and the lower the the first ionization energy is always
ionisation energy 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:

○ Across a period the nuclear charge increases

○ 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

○ The shielding by inner shell electrons remain reasonably constant as

electrons are being added to the same shell

○ It becomes harder to remove an electron as you move across a

period; more energy is needed

○ 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:
○ There is increased distance between the nucleus and the
outer electrons as you have added a new shell
○ There is increased shielding by inner electrons because
of the added shell
○ These two factors outweigh the Key word
increased nuclear charge
Shielding: the ability of inner
shell electrons to reduce the
effect of the nuclear charge on
outer shell electrons.
 Ionisation energy down a group
● The ionisation energy down a group decreases due to the following
factors:

○ The number of protons in the atom is increased, so the nuclear

charge increases

○ But, the atomic radius of the atoms increases as you are adding
more shells of electrons, making the atoms bigger

○ So, the distance between the nucleus and outer

electron increases as you descend the group
○ The shielding by inner shell electrons increases as there are
more shells of electrons

○ These factors outweigh the increased nuclear charge, meaning

it becomes easier to remove the outer electron as you
descend a group

○ So, the ionisation energy decreases

 Why there is a big difference
●
between some successive
For nitrogen, this occur between 5th and 6 IE.
th
IE
● For sodium, the big difference is between 1st and 2nd IE

● This large change indicate that for the second of these two IE, the
electron is being removed from a principal quantum shell closer to
the nucleus

● For eg. The 5th IE of nitrogen, the electron being removed from the
2nd principal quantum shell. For the 6th IE, the electron being
removed from 1st principal quantum shell.
 Additional resourses:

[Explaining Successive Ionisation

Energies]

Nitrogen www.youtube.com/watch?v=RDsC
WqckESA

2,5 [Successive ionisation energy / A

Level Chemistry]

www.youtube.com/watch?v=wAYzd
cmTXWo
Interpreting successive IE
What can we deduce from the graph?

● The 1st e- removed has low IE1.

That’s mean it is very easily
removed

● likely to be far away from nucleus

and well shielded by inner e-
shells.

● There is a big jump in IE2. The 2nd e-

much more difficult to removed
than the 1st e-

● This suggest that the 2nd e- is in

the shell closer to the nucleus
● The IE1 and IE2 suggest that Na has 1 e- in its
1st e- easily
outer shell removed
8 e- less
● From 2nd- 9th e- removed-IE gradually increase easily
removed
● Suggest that all 8 e- are in the same shell

● The 10th & 11th e- have extremely high IE.

Suggest that they are very close to the
nucleus Na

● Great force of attraction between nucleus and

these e-
nucleus
● There are no inner e- to shield them
2 e- very
● The large increase in IE between 9th and 10th difficult to
confirms that the 10th e- is in a shell closed to removed
the nucleus than 9th e-
 EXAMPLE
Based on the successive ionisation energy below, which group in the periodic
table does X belongs to?

Number of 1 2 3 4 5 6 7 8 9 10
e- removed
IE/kJ mol-1 1000 2260 3390 4540 7010 8500 27100 31670 36580 43140

Solution

1. Look for a large jump in IE value

2. Take the lower number (represent the number of e - that easily
removed)
3. Relate the number of outer shell e - to the group number
 2.3 Sub-shells and atomic orbital
Subshells (sub-level)
• The principal quantum shells are split into subshells which are given the letters s, p and d

• Elements with more than 57 electrons also have an f shell

• 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:
KEY-WORD

SUB-SHELLS (SUBSIDIARY
QUANTUM SHELLS):

Regions of the principal quantum

shells where electrons exists in
defined areas associated with
particular amount of energy.
 Atomic Orbitals
 Each shell can be divided further into subshells, labelled s, p, d and f

 Each subshell can hold a specific number of orbitals:

 s subshell : 1 orbital
 p subshell : 3 orbitals labelled p x, py and pz
 d subshell : 5 orbitals
 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:

 s : 1 x 2 = total of 2 electrons
 p : 3 x 2 = total of 6 electrons
 d : 5 x 2 = total of 10 electrons
 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 p x orbital is the same as a py orbital
KEY WORD

Atomic orbitals:
region of space
outside the nucleus
that can be
occupied by a
maximum of 2 e-
 Shapes of the orbital
s orbitals

● The s orbitals are spherical in

shape

● The size of the s orbitals increases

with increasing shell number

○ 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
 Shapes of the orbital
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
 t al
r bi
d o
f or
bi t a
l
 Filling the shells and orbital

• the most stable electronic configuration of an

atom is the one that has the lowest amount of
energy

• The order of sub-shells filled with e-, depends on

their relative energy

• So there is a sequence that we have to follow

• 1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s…

Additional info:
Energy Levels, Energy Sublevels, Orbitals, &
Pauli Exclusion Principle

www.youtube.com/watch?v=J-DjEIlynjE
 2.4 ELECTRONIC
CONFIGURATION
• 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
● Electrons can be imagined as small spinning charges which rotate around
their own axis in either a clockwise or anticlockwise direction

 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

 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

○ 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

○ 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
o The electron configuration can also be represented using the electrons in
boxes notation
o Each box represents an atomic orbital
o The boxes are arranged in order of increasing energy from lowest to highest
o 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

o The electrons in Titanium are arranged in their orbitals as shown. Electrons occupy
the lowest energy levels first before filling those with higher energy
 Example
Ca
20
1s
Sc
21
2s 2p
3s 3p 3d
4s 4p 4d 4f
5s 5p 5d 5f
Cr
24

Cu
29 Explaination:

https://www.youtube.com/watch?v=ZD5LOZvli6o
 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

○ Eg. a chlorine free radical has the

electron configuration 1s22s22p63s23p5

○ Two of the three p orbitals have paired

electrons whereas one of them has an
unpaired electron
Exam Tip
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. 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

○ The full electron configuration describes the arrangement of all

electrons from the 1s subshell up

○ 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

○ Negative ions are formed by adding electrons to the outer subshell

○ Positive ions are formed by removing electrons from the outer subshell

○ 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:

○ s block elements

■ Have their valence electron(s) in an s orbital

○ p block elements

■ Have their valence electron(s) in a p orbital

○ d block elements

■ Have their valence electron(s) in a d orbital

○ 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:

○ Cr is [Ar] 3d5 4s1 not [Ar] 3d4 4s2

○ Cu is [Ar] 3d10 4s1 not [Ar] 3d9 4s2

● This is because the [Ar] 3d 5 4s1 and [Ar] 3d10 4s1 configurations
are energetically stable
Example
Answer
● Answer 1: Potassium has 19 electrons so the full electronic
configuration is:

1s2 2s2 2p6 3s2 3p6 4s1

● The 4s orbital is lower in energy than the 3d subshell and is therefore filled
first

● The nearest preceding noble gas to potassium is argon which accounts for
18 electrons so the shorthand electron configuration is:

[Ar] 4s1
Answer 2: Calcium has 20 electrons so the full electronic configuration is:

1s2 2s2 2p6 3s2 3p6 4s2

● The 4s orbital is lower in energy than the 3d subshell and is therefore filled
first

● The shorthand version is [Ar] 4s2 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 Ca 2+ ion is identical to that of
argon

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

2 2 6 2 6
 2.5 periodic patterns of atomic and
Atomic radius ionic radii
● 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

● Atomic radii show predictable patterns across

the Periodic Table

○ They generally decrease across each

Period
The atomic radius of a hydrogen atom is
determined by halving the distance
○ They generally increase down each Group
between the nuclei of two hydrogen atoms
covalently bonded
● These trends can be explained by the electron shell theory

○ 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

○ The larger the nuclear charge, the greater the pull of the nuclei on the
electrons which results in smaller atoms

○ Atomic radii increase moving down a Group as there is an increased

number of shells going down the Group

○ The electrons in the inner shells repel the electrons in the outermost
shells, shielding them from the positive nuclear charge

○ 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

○ 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

○ Ionic radii increase with increasing negative charge

○ Ionic radii decrease with increasing positive charge

● These trends can also be explained by the electron shell theory

○ Ions with negative charges are formed by atoms accepting extra

electrons while the nuclear charge remains the same

○ 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
○ The greater the negative charge, the larger the ionic radius

○ Positively charged ions are formed by atoms losing electrons

○ 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

○ The greater the positive charger, the smaller the ionic radius
Trends in the ionic radii across a
period and down a group
 Interpreting line emission spectra
n=6
n=5
n=4
energy

n=3

n=2

n=1
Frequency increase
Line
emission
spectum
AB C D E FG H I
1 series of lines
st
2nd series of lines

Part of the line emission spectrum and the corresponding electron

energy levels
● A) in the diagram, what do the letters n represent?

The principal energy levels

● B) describe how the spacing of each series of lines changes as the frequency
increases

The spacing gets smaller / the lines get closer together.

● C) what do the vertical arrow represent?

Electrons falling from higher to lower energy levels

● D) which line in the spectrum represents the greatest energy change?

● E) which line in the spectrum represent the smallest energy change?

I
● F) what happens to the distance between the energy levels as they get
further from the nucleus

The energy levels get closer.

● G) which line represents an electron falling from the fourth energy level to
the second energy level

● H) suggest, using information in the diagram, why the first ionisation energy
of Li is much lower that the 1st IE of hydrogen.

It takes more energy to remove the electron from hydrogen as the

electron is at a lower energy level closer to the attractive force of the
nucleus / it takes less energy to remove the outer electron from a lithium
atom since the outer electron is further from the attractive force of the
nucleus.
 Summary
● electron shells can be divided into s, p, and d subshells which can hold a maximum of
2.6. and 10 electrons respectively. And each sub-shells has a specific number of orbitals
which can each hold a maximum of two electrons.
● The first IE of an element is the energy needed to remove 1 e- from each atom in one
mole of atoms of the element in the gaseous state
● The magnitude of IE depends on 4 factors

○ The distance of e- from the nucleus

○ The number of positive charge in nucleus

○ The degree of shielding of outer e- by inner e- shells

○ Spin-pair repulsion
● The electronic configuration of the outer shell electrons and the position of an element
in the periodic table can be deduce using successive ionisation energy data.
 Thanks
!

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