Atomic Structure Boardworks 1

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Subatomic particles
Atoms are composed of three subatomic particles: protons,
neutrons and electrons. The two important properties of
these particles are mass and charge:
Relative Relative
Particle
mass charge
proton 1 +1
neutron 1 0
electron 1/1840 -1
The mass of electrons is negligible when compared to the

mass of protons and neutrons, so their mass is not included
when calculating the mass of the atom.

Atomic number and mass number
The number of protons in an atom is known as the
atomic number or proton number and is represented
by the symbol Z.
The mass number of an atom is the number of protons

plus the number of neutrons, and is represented by the
symbol A.
When an atom is mass

represented by its number (A)
symbol, the mass
number, and atomic
sometimes the atomic number (Z)
number, are shown.

What are isotopes?
Isotopes are atoms of the same element that contain
different numbers of neutrons.
mass number
is different
atomic number
is the same
carbon-12 carbon-13
The reactivity of different isotopes of an element is identical

because they have the same number of electrons.
The different masses of the atoms means that physical
properties of isotopes are slightly different.

Isotopes of chlorine
About 75% of naturally-occurring chlorine is chlorine-35 (35Cl)
and 25% is chlorine-37 (37Cl).
17 protons 17 protons
18 neutrons 20 neutrons
17 electrons 17 electrons

Isotopes of carbon
There is also more than one isotope of carbon:
Isotope Protons Neutrons

12
C 6 6
13
C 6 7
14
C 6 8
All isotopes of carbon have 6 protons and so have 6

electrons.
Because chemical reactivity depends on the number of
electrons the reactivity of the isotopes of carbon is identical.

What’s the number?

‘Weighing’ atoms
Mass spectrometry is an accurate instrumental technique
used to determine the relative isotopic mass (mass of each
individual isotope relative to carbon-12) and the relative
abundance for each isotope. From this, the relative atomic
mass of the element can be calculated.
Some uses of mass

spectrometry include:
 carbon-14 dating
 detecting illegal drugs
 forensic science
 space exploration.

Mass spectrometry

Parts of the mass spectrometer

Process of mass spectrometry

Mass spectra of monatomic elements

Mass spectra of diatomic elements

Process of mass spectrometry

What is relative atomic mass?
The relative atomic mass (Ar) of an element is the mass of
one of its atoms relative to 1/12 the mass of one atom of
carbon-12.
relative atomic mass average mass of an atom × 12
=
(Ar) mass of one atom of carbon-12
Most elements have more

than one isotope. The Ar of
the element is the average
mass of the isotopes taking
into account the abundance of
each isotope. This is why the
Ar of an element is frequently
not a whole number.

Using mass spectra to calculate Ar
The mass spectrum of an element indicates the mass and
abundance of each isotope present. For example, the mass
spectrum of boron indicates two isotopes are present:
100
abundance (%)
80
11
B (80%)
60
40 10
B (20%)
20
0
0 2 4 6 8 10 12
m/z
How can this be used to calculate the Ar of boron?

Calculating Ar
Most elements have more than one isotope. The relative
atomic mass of the element is the average mass of the
isotopes taking into account the abundance of each isotope.
Example: what is the Ar of boron?

In a sample of boron, 20% of the atoms are 10Br and 80%
are 11Br.
If there are 100 atoms, then 20 atoms would be 10Br and
80 atoms would be 11Br.
The relative atomic mass is calculated as follows:
Ar of Br = (20 × 10) + (80 × 11)
100
Ar of Br = 10.8

Calculating Ar of magnesium
In a sample of magnesium, 79.0% of the magnesium
atoms are 24Mg, 10.0% are 25Mg and 11.0% are 26Mg.
Example: What is the Ar of magnesium?

1. Calculate mass × abundance 24 × 79.0
of each isotope
25 × 10.0
26 × 11.0
2. Add these values, (1896 + 250 + 286) / 100

and divide by 100
Ar of Mg = 24.3

Ar calculations

Glossary

What’s the keyword?

Multiple-choice quiz

Models of atoms
At GCSE level, the model of the
atom states that a nucleus is
surrounded by shells of electrons.
Each shell holds a different
maximum number of electrons:
 1st shell = 2 electrons

 2nd shell = 8 electrons
 3rd shell = 8 electrons.
At A-level, this model is slightly different. Instead of electrons

being arranged in shells that are a different distance from the
nucleus, they are arranged in energy levels.

The Bohr model of the atom
In 1900, Max Planck
(right) developed his
‘Quantum theory’, which
states that energy exists
in fixed amounts called
quanta.
In 1913, Niels Bohr (left)

applied Plank’s theory to
electrons. He proposed that electrons could only exist in
fixed energy levels.
The main energy levels are called principal energy levels

and are given a number called the principal quantum
number (n) with the lowest in energy being 1.

What is ionization energy?
Ionization is a process in which atoms lose or gain electrons
and become ions.
The first ionization (I1) energy of an element is the energy

required to remove one electron from a gaseous atom.
M(g) → M+(g) + e-(g)
The second ionization (I2) energy involves the removal of a

second electron:
M+(g) → M2+(g) + e-(g)
Looking at trends in ionization energies can reveal useful

evidence for the arrangement of electrons in atoms and ions.

Ionization energy definitions

Evidence for energy levels
Plotting the successive ionization energies of magnesium
clearly shows the existence of different energy levels, and
the number of electrons at each level.
6
Successive ionization
energies increase as more
ionization energy
5 electrons are removed.
4 Large jumps in the ionization

energy reveal where electrons
are being removed from the
3 next principal energy level,
such as between the 2nd and
2 3rd, and 10th and 11th ionization
th
th
th
2 nd
3 rd
4 th
5 th
6 th
7 th
8 th
9 th
1 st
energies for magnesium.

10
11
12
electron removed
More evidence for energy levels
The first ionization energies of group 2 elements also show
evidence for the existence of different principal energy levels.
900 Even though the nuclear

first ionization energy
charge increases down the

800 group, the first ionization
energy decreases.
(kJ mol-1)
700
This means electrons are
600 being removed from
successively higher
500 energy levels, which lie
further from the nucleus
400
and are less attracted to
Be Mg Ca Sr Ba
the nucleus.
element
Trends in first ionization energies

Energy levels

Evidence for sub-levels
1600 The first ionization
energies for the elements

1400
in period 3 show a
1200 general increase.
(kJ mol-1)
1000
However, aluminium’s
800 value is below that of
600 magnesium. This suggests
that the third principal
400 energy level is not one
Na Mg Al Si P S Cl Ar
single energy level.
element
All principal energy levels contain one or more sub-levels,
with different but exact energy values.

The sub-levels
There are four sub-levels, sub-level max no. electrons
labelled in order of
s 2
increasing energy: s, p, d
and f. Each holds a p 6
different number of d 10
electrons. f 14
Each principal principal energy sub-levels max no.

energy level level, n electrons
contains a 1 1s 2
different
2 2s, 2p 8
number of
sub-levels. 3 3s, 3p, 3d 18
4 4s, 4p, 4d, 4f 32

Levels and sub-levels

Blocks of the periodic table

Order of sub-levels

The Aufbau principle
As part of his work on electron configuration, Niels Bohr
developed the Aufbau principle, which states how
electrons occupy sub-levels.
The Aufbau principle states that the

lowest energy sub-levels are occupied first.
This means the 1s sub-level

is filled first, followed by 2s,
2p, 3s and 3p.
However, the 4s sub-level is

lower in energy than the 3d,
so this will fill first.

Writing electron configuration

Electron configuration: true or false?

Electron configuration of transition metals
Although the 3d sub-level is in
a lower principal energy level
than the 4s sub-level, it is
actually higher in energy.
This means that the 4s sub-level

is filled before the 3d sub-level.
Example: what is the electron structure of vanadium?

1. Count number of electrons in atom 23
2. Fill sub-levels, remembering 1s22s22p63s23p64s23d3
4s is filled before 3d

Electronic configuration: atoms

Electron configuration of ions
When writing the electron
configuration of ions, it is For negative ions
important to add or subtract the add electrons.
appropriate number of electrons.
For positive ions
remove electrons.
For non-transition metals, the sub-
levels are then filled as for atoms.
Example: what is the electron structure of O2-?

1. Count number of electrons in atom 8
2. Add or remove electrons due to charge 8 + 2 = 10
3. Fill sub-levels as for uncharged atom 1s22s22p6

Electronic configuration of transition metal ions
When transition metals form ions, it is the 4s electrons that

are removed before the 3d electrons.
Example: what is the electron structure of Ni2+?

1. Count number of electrons 28
in atom
2. Fill sub-levels, remembering 1s22s22p63s23p64s23d8
4s is filled before 3d
3. Count number of electrons 2
to be removed
4. Remove electrons starting 1s22s22p63s23p63d8
with 4s

Electron configuration: ions

Electron orbitals
It is impossible to exactly locate the position of an electron
within an energy sub-level. By measuring the electron density
around the nucleus, it is possible to define regions where
electrons are most likely to be found at any one time. These
regions are called orbitals.
Each energy sub-level has one or more orbitals, each of
which can contain a maximum of two electrons.
sub-level no. orbits max no.
electrons
s 1 2
p 3 6
d 5 10
f 7 14
Shapes of electron orbitals

The Pauli exclusion principle and spin
The Pauli exclusion principle states that each orbital

may contain no more than two electrons.
It also introduces a property of electrons called spin, which

has two states: ‘up’ and ‘down’. The spins of electrons in the
same orbital must be opposite, i.e. one ‘up’ and one ‘down’.
A spin diagram shows

how the orbitals are spin diagram
filled. Orbitals are for
represented by squares, magnesium,
and electrons by arrows 1s22s22p63s2
pointing up or down.

Rules for filling electrons
When two electrons
occupy a p sub-level,
they could either
completely fill the same
p orbital or half fill two
different p orbitals.
Hund’s rule states that single electrons

occupy all empty orbitals within a sub-level
before they start to form pairs in orbitals.
If two electrons enter the same orbital there is repulsion

between them due to their negative charges. The most stable
configuration is with single electrons in different orbitals.

Evidence for Hund’s rule
The first ionization energies for the elements in period 3 show
a general increase.
1600
However, sulfur’s value

1400 is below that of
1200 phosphorus. As the
(KJ mol-1)
highest energy
1000 electrons of both are in
800 the 3p sub-level this is
evidence for Hund’s
600 rule.
400
element
Evidence for Hund’s rule: P vs. S
Phosphorus has three electrons in its 3p sub-level and
sulfur has four.
The lower first ionisation energy for sulfur is because it has

a pair of electrons in one of the 3p orbitals. Mutual repulsion
between these two electrons makes it easier to remove one
of them.
phosphorus sulfur

Electron configuration of Cr and Cu
The electron configurations of chromium and copper are
exceptions to the normal rules of orbital filling:
chromium copper
1s22s22p63s23p64s13d5 1s22s22p63s23p64s13d10
In each case the 4s orbital contains one electron. This is

because the 4s and 3d sub-levels lie very close together in
energy, and the 3d being either half full or completely full is a
lower energy arrangement.
With larger atoms like this it can be useful to shorten the

electron arrangement. Copper can be shortened to
[Ar]4s13d10.

Creating spin diagrams

Glossary


Energy levels and electrons


What is periodicity?
The term periodicity describes a repeating pattern in
properties of elements across periods of the periodic table.
The Russian chemist Dmitry

Mendeleev is credited with being the
creator of the first version of the
periodic table. He observed that when
the elements are arranged in order of
atomic mass, there are recurring
patterns in certain properties.
The modern periodic table can be used

to analyse trends in properties such as
atomic radius across periods and
down groups.

What is atomic radius?
The atomic radius of an element is difficult to precisely define
because of the uncertainty over the size of the electron cloud.
Several definitions are used.
One definition is half the shortest internuclear distance found

in the structure of the element.
For non-metallic elements, the

covalent radius is often used
as the atomic radius. This is half
the internuclear distance covalent
between two identical atoms in radius
a single covalent bond.

More on atomic radius
For non-bonded adjacent atoms (e.g. in a covalent crystal of
a non-metallic element), the van der Waals radius is used
as a value for atomic radius. This is half the shortest
internuclear distance between two similar non-bonded atoms.
van der
Waals radius
For metallic elements, the metallic radius is often used as

the atomic radius. This is half the shortest internuclear
distance between two adjacent atoms in a metallic bond.

Trends in atomic radius in period 3

Trends in atomic radius in period 3
Atomic The atomic radius of the elements

Element across period 3 decreases.
radius (nm)
Na 0.190 This might seem counter-
Mg 0.145 intuitive, because as the
numbers of sub-atomic particles
Al 0.118
increase, the radius might be
Si 0.111 expected to also increase.
P 0.098
However, more than 99% of the
S 0.088
atom is empty space – the
Cl 0.079 nucleus and electrons themselves
Ar 0.071 occupy a tiny volume of the atom.

Increase in proton number
The number of protons in the nucleus of the atoms
increases across period 3.
proton Element 11 Na 12 Mg 13 Al 14 Si 15 P 16 S 17 Cl 18 Ar
number
This increase in the number of protons increases the

nuclear charge of the atoms. The nucleus has stronger
attraction for the electrons, pulling them in closer and so
the atomic radius decreases across the period.
increased
nuclear charge
pulls electrons
closer

What is shielding?

Explaining atomic radius in period 3
Atomic Proton number increases

Proton across period 3, but
Element number radius
(nm) shielding remains
approximately constant.
Na 11 0.190
Mg 12 0.145 This causes an increase
Al 13 0.118 in effective nuclear
charge, leading to a
Si 14 0.111 greater attraction
P 15 0.098 between the nucleus and
the outermost electrons.
S 16 0.088
Cl 17 0.079 This pulls these electrons
closer to the nucleus and
Ar 18 0.071 results in a smaller radius.

Atomic radius in period 3

Atomic radius: true or false?

What is first ionization energy?
Ionization is a process in which atoms lose or gain electrons
and become ions.
The first ionization energy of an element is the energy

required to remove one electron from a gaseous atom.
M(g) → M+(g) + e-
The first ionization energy is therefore a measure of the

strength of the attraction between the outermost electrons
and the nucleus.
The first ionization energies of the elements in periods 2

or 3 can give information about their electronic structure.

Plot of the first ionization energies

General trend in first ionization energy
There is a general 1600
increase in the first 1400
ionization energy
ionization energies 1200
(kJ mol-1)
across period 3. 1000
800
Across period 3, the
600
proton number
increases but the 400
amount of shielding
element
does not change significantly.
The effective nuclear charge therefore increases.
The greater attraction between the nucleus and the

outermost electrons means that more energy is required to
remove an electron.

Trend in first ionization energy: exceptions
There are two exceptions to the general trend in first
ionization energy: both aluminium and sulfur have lower
ionization energies than might be expected.
1600
energy (kJ mol-1)
1400 lower
ionization
1200 ionization
1000 energies
800 than
expected
600
400
element

First ionization energy of Al vs. Mg
The first ionization energy of aluminium is less than that
of magnesium, even though aluminium has a higher
nuclear charge.
The electron removed when aluminium is ionized is in a 3p
sub-level, which is higher in energy than the 3s electron
removed when magnesium is ionized. Removing an
electron from a higher energy orbital requires less energy.
magnesium aluminium

First ionization energy of S vs. P
The first ionization energy of sulfur is less than that of
phosphorus, even though sulfur has a higher nuclear charge.
The highest energy electron in both phosphorus and sulfur is

in the 3p sub-level. However, in sulfur this electron is paired,
while in phosphorus each 3p orbital is singly occupied.
Mutual repulsion between paired electrons means less
energy is required to remove one of them.
phosphorus sulfur

Ionization energy in period 3

Ionization energy in period 3

Plot of the melting and boiling points

Na, Mg and Al: melting and boiling points
The melting and boiling points increase for the three metallic
elements from sodium to aluminium.
3000
This is because the
2500
temperature (K)
strength of the
2000 metallic bonds
boiling point
1500 increases. More
energy is needed to
1000 break the stronger
melting point
500 metallic bonds, so
0 melting and boiling
Na Mg Al points are higher.
element

Na, Mg and Al: metallic bond strength
The increase in metallic bond strength from sodium to
aluminium is due to two factors:
1. Charge density. This is the ratio of an
ion’s charge to its size. Na+ ions are
large with a small charge, so have a
low charge density. Al3+ ions are
smaller with a larger charge, and so
have a higher charge density. They are
therefore more strongly attracted to the
delocalized electrons.
2. Number of free electrons. Sodium has one
free electron per metal ion, whereas
aluminium has three. This leads to more
attractions that must be broken in aluminium.

Silicon
Silicon has a macromolecular
structure similar to that of
diamond.
Each silicon atom is

bonded to four
neighbouring silicon atoms
by strong covalent bonds.
These must be broken in
order for silicon to melt.
This requires a lot of
energy, so silicon's melting
and boiling points are high.

Period 3 non-metals
The melting and boiling points of phosphorus, sulfur and
chlorine are much lower than those of silicon.
3500
This is because 3000
temperature (K)
they have a 2500
simple molecular 2000
structure with 1500
weak van der 1000
Waals forces 500
holding the 0
molecules together. Na Mg Al Si P S Cl Ar
element
Breaking these forces of attraction requires much less
energy than breaking covalent bonds.

Period 3 non-metals: structure

Melting points in period 3

Melting points in period 3

Glossary




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1 of 26 © Boardworks Ltd 2009

The mass of electrons is negligible when compared to the

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The mass number of an atom is the number of protons

When an atom is mass

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The reactivity of different isotopes of an element is identical

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Isotope Protons Neutrons

All isotopes of carbon have 6 protons and so have 6

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Some uses of mass

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Most elements have more

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Example: what is the Ar of boron?

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Example: What is the Ar of magnesium?

2. Add these values, (1896 + 250 + 286) / 100

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 1st shell = 2 electrons

At A-level, this model is slightly different. Instead of electrons

28 of 39 © Boardworks Ltd 2009

In 1913, Niels Bohr (left)

The main energy levels are called principal energy levels

29 of 39 © Boardworks Ltd 2009

The first ionization (I1) energy of an element is the energy

M(g) → M+(g) + e-(g)

The second ionization (I2) energy involves the removal of a

Looking at trends in ionization energies can reveal useful

30 of 39 © Boardworks Ltd 2009

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5 electrons are removed.

4 Large jumps in the ionization

energies for magnesium.

900 Even though the nuclear

charge increases down the

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energies for the elements

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Each principal principal energy sub-levels max no.

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The Aufbau principle states that the