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A Sam Ellis Academy Document

AQA A-LEVEL CHEMISTRY | 3.1.1 - Atomic Structure

Written by Sam Ellis and Hilary Meng in 2022

There is no copyright restrictions, you can distribute this document
freely.

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3.1.1 - Atomic Structure

Fundamental Particles
Atom: the smallest particle of an element which has the characteristic,
(chemical and physical) properties of that element.

Relative mass of subatomic particles

Atoms are made of smaller particles: protons, neutrons, &
electrons

These 3 particles are fundamental

Atoms of different elements are made of different combinations of the

three (that’s why different elements have different relative masses!)

This table tells you everything you need to know about protons, neutrons,
& electrons

• As you can see, the relative mass of an electron is negligible (Very

small). This means most of the mass of an atom is concentrated in the
nucleus. You find this right in the middle; the nucleus is only a tiny
fraction of the atoms total volume.

• The incredibly high density of the nucleus suggests that the particles
inside it are held very close together by an extremely powerful force,
Protons are positively charged, so without this force the positive—
positive repulsion would lead to the nucleus essentially exploding.

• If you do A-Level physics, you’ll learn about this force (the Strong
Nuclear Force) If you’re just doing A-Level Chemistry, just an
appreciation of its existence is enough!

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Mass Number and Isotopes

Atomic number: The number of protons in the
nucleus of an atom. Denoted by Z

Mass number: The number of protons +

neutrons in the nucleus Denoted by A

Isotopes: atom with a different no. of

neutrons but same no. of protons.

Relative Atomic mass: the mass of a single

atom of an element relative to 1/12 mass of
an atom of carbon-12.

Relative isotopic mass: the mass of a

single
isotope of an element relative to 1/12 mass
of an atom of carbon-12.

Time-of-flight (TOF) mass spectrometer

A T.O.F. Mass spectrometer is used to identify elements and determine
relative molecular masses. It gives accurate information about relative
isotopic mass and also about relative abundance of isotopes.

There’s four stages you need to be able to detail in the exam and,
because we just love to help you out, they're listed and explained below.

Something to note, all the ions talked about in A-Level Chemistry TOF
mass spectrometry are ions with a 1+ Charge; in real life, you can of
course have 2+, 3+… you get the idea.

1) Ionisation: There’s two types!

Electrospray ionisation:
- The sample is dissolved in a volatile solvent and injected through a
fine hypodermic needle (Very fine needle) giving a fine mist.
- A high voltage is applied to the tip of the needle, causing each
particle to gain a proton as it leaves the needle.
- The solvent evaporates (and is therefore removed) producing gaseous,
positive ions.

Electron impact ionisation:

- The sample is vaporised
- an ‘electron gun’ (which is just an exposed filament of wire) is
used to fire high energy electrons at the sample.
- This knocks one electron off each particle, so they become +1 ions.

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2) Acceleration:
- An electric field is applied to give all the ions with the same
charge a constant kinetic energy.
- As KE = 0.5mv2, Kinetic energy of the ions only depends on the mass
(m) of the particles and their velocity (V).
- As all particles are given the same KE, heavier particles (larger Mr
with a bigger m) move more slowly than lighter particles.

3) Ion drift:
- The ions enter a region with no electric field called the flight
tube.
- Here the ions are separated based on their different velocities; the
heavier ions have less KE (Move less quickly) compared to the smaller
ions (which travel quicker) and arrive at the detector first.

4) Ion detection:

- The detector records the different flight times of the ions. The
positively charged ions arrive at the detector and gain an electron,
inducing a current in the detector
- It’s important to know that the more abundant a given Ion is, the
larger the current it induces. This means a bigger peak in the
spectrum (more on this on the next page)

General information about a mass spectrum

This is what the machine gives you after those four Stages. It’s a series
of peaks on a graph. The vertical axis is relative abundance and the
horizontal axis is the m/z (Mass / Charge)

The relative abundance is a measure of how many of each ion is present.

Often the highest peak (known as the base peak) is given a value of 100
and the other peaks are worked out relative to this value.

The m/z for a single charge ion = mass of the ion, as mass divided by 1 =
mass. The m/z values for isotopes of an element are the relative isotopic
masses for these isotopes.

Mass spectrum of an element: Magnesium

The peaks in the spectrum are caused by the different isotopes of Mg.

The mass spectrum tells us several things:

1) Mg = 3 peaks = 3 isotopes.
2) The relative isotopic masses of these are
24, 25 + 26 = the m/z values of each of the
isotopes.
3) The most abundant isotope of Mg = relative
isotopic mass of 24. This is the m/z value
for the base peak.
4) The ion responsible for the peak at: 24 is
24Mg+; 25 is 25Mg+; at 26 is 26Mg+.
5) The relative atomic mass (Ar) of Mg can be
calculated using info. in the mass spectrum.
Simply find the mean of all the atoms of the
different isotopes.
- E.g. relative atomic mass = ((100x24) +
(8.9x25) + (10.9x26))/119.8 = 24.26 = 24.3 (1 d.p.)

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Mass spectrum of a molecular element: Chlorine

Cl exists as diatomic molecules (Cl2). the molecules of an element like
Cl can form ions with a single positive charge but the molecules can also
be broken up into atoms. These atoms go on to form single Positively
charged ions of themselves; see below.

Cl has 2 isotopes: 35Cl and 37Cl.

So, there are 5 different possible ions which should be detected in the
mass spectrometer:
• 35Cl+
• 37Cl+
• (35Cl-35Cl)+
• (37Cl-37Cl)+
• (35Cl-37Cl)+
there should be peaks seen at m/z
values of 35, 37, 70, 72 and 74 on a
mass spectrum of molecular Cl and there
is!

Mass spectrum of a compound: Ethanol

For a compound: the last major peak, at
the highest m/z value, is the molecular
ion. The m/z value of this peak is the
relative molecular mass (Mr) of the base peak →
compound.

in this case, as the molecular ion peak

has an m/z value of 46, the Mr of Mr of
ethanol = 46. compound→
- The base peak is usually not the
molecular ion peak.
- There is a small peak at 47 and this
is caused by the presence of one 13C
atom in the ethanol molecule (C2H6O)

Electron Configuration
Principle energy levels = shells.

Basic information
• 1st energy level (moving out of nucleus) is called n=1; 2nd n=2 etc.
This no. is called the principal quantum number.
• The energy levels get closer together as you move further from the
nucleus. Distance between n=1 and n=2 is larger than the distance
between n=2 and n=3. This cont. further from the nucleus.
• Each energy level is divided into sub-shells: contains an orbital or a
combination of orbitals.
• Orbital: a 3-D space + each orbital can hold up to 2 electrons.
• 2 electrons in the same orbital spin in opp. directions to minimise
repulsions.

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The sub-shells
Evidence of existence of sub-shells comes from ionisation energies of
elements. A sub-shell/-level is always written as the energy level
(principle quantum no.) + then the type of orbital which makes up that
sub-shell.

There are 3 types of orbitals we need to know: s, p, d

Each holds a different number of e-:
s = 2 Increasing
Energy
p = 6
d = 10

Principle Energy Level Sub-levels

1 1s
Overlap →
2 2s,2p
3 3s,3p,3d
4 4s,4p,4d,
4f

The Aufbau Principle

You probably won’t have heard the name, but you do need to know the
principle. It states that the lowest energy sub-levels are occupied
first. Below and above on that graph is the order

1s
2s 2p
3s 3p 3d So, the order is: 1s 2s 2p 3s 3p 4s 3d 4p
4s 4p …

Writing notations for electrons in sub-shells

When electrons are exist in a sub-shell, a number (written as a
superscript, which means above it) is written after the sub-shell
notation (this will make sense below)

Sub-shells at the same energy level should be written together in a

sequence. So although the 4s fills before the 3d, as it has a slightly
lower energy level than the 3d sub-shell, in written form the 3d should
always be written before the 4s. This means a scandium atom would be

1s22s22p63s23p63d14s2.

That example demonstrate everything you need to know about writing in

this notation!

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Shortened electron configurations

Noble gas symbols in square brackets, such as [Ar], are sometimes used as
shorthand in electron configurations. E.g. calcium (1s22s22p63s23p64s2) can
be written as [Ar]4s2, where [Ar] = 1s22s22p63s23p6. This isn’t tested
often but when if it is, it’s easy for you now!

A typical sub-shell diagram

Very important for you to understand the following from the diagram of
the electron configurations of potassium (K):

• 4s sub-shell is at a lower energy level than the 3d sub-shell ∴ 4s

fills before 3d.
• The electrons are indicated by ↿ and ⇂. They represent the different
directions of spin (Don’t worry about this too much, just do them the
opposite way in the same box!)

When electrons are in their lowest possible energy levels, the atom is
said to be in the ground state.

NOTE: Electrons repel each other, so will only form pairs in an orbital
when they have to.

s, d, p block elements
Elements can be classified as s block, p
block or d block elements. depending on where they
are in the periodic table and which sub-shell
their outer. electrons are in.

Ionisation Energies
The electrons in atoms and ions are attracted to the positive nucleus.
Energy is required to overcome this attraction and remove electrons.
Ionisation is the process of removing electrons

First ionisation energy: energy required to remove 1 mole of electrons

from 1 mole of gaseous atoms, forming 1 mole of gaseous ions with a
charge of +1.
- Successive ionisations give the 1st, 2nd, 3rd, etc. ionisation
energies. Only 1 mole of electrons is removed with each ionisation.

E.g. for sodium…

The 1st ionisation energy of Na = the equation: Na(g) → Na+(g) + e-
The 2nd ionisation energy of Na = the equation: Na+(g) → Na2+(g) + e-
The 3rd ionisation energy of Na= the equation: Na2+(g) → Na3+(g) + e-

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Values for ionisation energies

Measured in kJmol-1. All ionisation energy values will be +ve as they are
endothermic as energy is required to remove an electron from the
attractive power of the nucleus. The higher the value, the more energy is
required to remove 1 mole of electrons.

Ionisation energies as evidence for energy levels

This graph shows the successive ionisation energies of a Na atom. It
becomes clear from the graph that there is a distinct set of energy
levels…
- The log of the ionisation energy is used to condense the diagram as the
ionisation energies vary across a wide range of values.

General ↑ in successive ionisation energy

values due to ↑ in effective nuclear
charge i.e. ratio of protons to electrons ↑

Large gap between 9th +

10th electrons as 10th =
removed from an energy
level closer to the nucleus
Large gap between 1st +
2nd electrons as 2nd =
removed from an energy
level closer to the nucleus

The existence of energy levels is proven by the large gaps in the

successive ionisation energies as these correspond to the removal of
electrons from energy levels closer to the nucleus + so more energy is
required to remove the electron.

Using successive ionisation energies

Successive ionisation energies are an indicator of the group to which an
element belongs.

Ionisation energy pattern for elements 1 (H) to 36 (Kr)

There are 3 general patterns that should be apparent from the graph:
1) Ionisation energy decreases down
a group. First ionisation energies for the elements H to
↓ from He ➜ Ne ➜ Ar ➜ Kr. Xe
2) Ionisation energy shows a general
increase across a period.
From Na ➜ Ar there is a general
↑ in 1st ionisation energy.
3) W/in the short periods (2 and 3),
there is a zig-zag pattern.
1st ionisation energy drops below
the general ↑ for elements in
group 3 (B and Al) and group 6 (O
and S).

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Explaining trends in ionisation energies

The patterns in ionisation energies can be explained by the electronic
structures of the atoms. 3 main factors which can be used to explain
these patterns are…
…Atomic radius
• Atomic radius ↑ down a group + ↓ across a period.
• The further an outer electron is from the attractive power of the
nucleus the less energy required to ionise it.
…Nuclear charge
• The greater the no. of protons, the greater the nuclear charge.
• A greater nuclear charge leads to a stronger attraction to the outer
electron, so more energy is required to ionise it.
…Shielding by inner electrons
• The attractive power of the nucleus can be shielded by inner electrons.
• The more inner electrons there are, the more the nucleus is shielded +
the less energy is required to ionise the outer electron.

First ionisation energy decreases down a group

• Atomic radius ↑ - outer electrons are further away from the nucleus (at
higher energy levels), so held less strongly by nucleus.
• Shielding from nuclear charge by inner electrons ↑
• Less energy required to remove the electrons ∴ 1st ionisation energy ↓

First ionisation energy increases across a period

• Atomic radius ↓- outer electrons are closer to the nucleus (at lower
energy levels), so held more strongly by nucleus.
• Nuclear charge ↑
• Shielding by inner electrons is the same (as outer electron is in the
same energy level).
• More energy required to remove the electrons ∴ 1st ionisation energy ↑

Lower first ionisation energy than expected for elements in

Group 3 and Group 6
Atoms of elements in group 3 and 6 show a lower 1st ionisation energy
than would be expected. This gives us evidence that 2nd + 3rd energy
levels are divided into 2 sub-shells, the 1st taking 2 electrons and the
2nd taking 6, ∴ proving sub-shells exist.
• Group 3 electrons have an s2p1 arrangement
- Outer p1 electron is further from the nucleus.
- Inner s2 electrons ↑ shielding so less energy is required to ionise
the outer p1 electron
- ∴ 1st ionisation energy ↓
• Group 6 atoms have a p4 arrangement
- The repulsion of 2 electrons in the same p orbital leads to less
energy being required to ionise the outer electron.
- ∴ 1st ionisation energy ↓

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Group 1 and Group 0 elements

• Atoms of group 1 elements have the lowest 1st ionisation energy in
every period as they have the greatest atomic radius + the lowest
nuclear charge in a particular period.
• Atoms of group 0 elements have the highest 1st ionisation energy in
every period as they have the smallest atomic radius + the highest
nuclear charge in a period.

Patterns in second ionisation energies

Patterns in 1st ionisation energies are shifted one to the left when the
patterns of 2nd ionisation energies are considered. Where a group 1
element would have the lowest 1st ionisation energy, it would have the
highest 2nd ionisation energy.
- Group 1 elements have the highest 2nd ionisation energy in a particular
period as the 2nd electron is being removed from an energy level closer
to the nucleus. Group 2 elements have the lowest 2nd ionisation energy
in a particular period.

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