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AQA – Atomic Structure

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What the spec says

• Appreciate that • Mass number (A) and atomic (proton) number
(Z).
• Electron configurations of
knowledge and • Students should be able to:
atoms and ions up to Z = 36 in
terms of shells and sub-shells
understanding of atomic • • determine the number of fundamental
particles in atoms and ions using mass number, (orbitals) s, p and d.
structure has evolved atomic number and charge
• Ionisation energies.
over time. •
• • explain the existence of isotopes.
The principles of a simple time of flight (TOF) • Students should be able to:
• Protons, neutrons and mass spectrometer, limited to ionisation,
acceleration to give all ions constant kinetic
• • define first ionisation energy
electrons: relative charge energy, ion drift, ion detection, data analysis.
• The mass spectrometer gives accurate • • write equations for first and
and relative mass. information about relative isotopic mass and
successive ionisation energies
also about the relative abundance of isotopes.
• An atom consists of a • Mass spectrometry can be used to identify • • explain how first and
elements.
nucleus containing • Mass spectrometry can be used to determine
successive ionisation energies
protons and neutrons relative molecular mass. in Period 3 (Na–Ar) and in
surrounded by electrons. • Students should be able to: Group 2 (Be–Ba) give evidence
• • interpret simple mass spectra of elements • for electron configuration in
calculate relative atomic mass from isotopic
abundance, limited to mononuclear ions. sub-shells and in shells.
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Nucleus
The Atom Mass Number
Tells us the number of
protons and neutrons in the
Most of the mass of an atom
e nucleus
and very small. Contains
protons and neutrons
N P N
N P P 7
N Electrons

Li
Orbit the nucleus in shells
and take most of the space of
e an atom.
e

Subatomic Relative Relative

Particle Charge Mass 3 Atomic (proton) number
Proton +1 1 Tells us the number of
P
Neutron 0 1 protons in the nucleus.
N Remember all atoms are neutral so
Electron -1 1/2000 the number of protons = number
e of electrons.
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Ions and Isotopes

Isotopes – elements with the same number of protons but
Ions have a different number of electrons and protons. a different number of neutrons

Negative ions
O2-
E.g. O2- have gained electrons to 12 13 14
gain a full shell of electrons and

C C C
P = 8 Charge +8
enable to form a more stable N = 8 Charge 0
ionic compound. e = 10 Charge -10
Total charge = -2

Positive ions Na+ 6 6 6

E.g. Na+ have lost electrons to
P = 11 Charge +11 P= 6 P= 6 P= 6
gain a full shell of electrons and
N = 12 Charge 0
enable to form a more stable
e = 10 Charge -10 N= 6 N= 7 N= 8
ionic compound. e= 6 e= 6
Total charge = +1 e= 6
Different number of neutrons
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Same number of protons
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History of the atom Positive
nucleus
1909 Ernest Rutherford Gold leaf experiment
Negative
1803 John Dalton Positive alpha particles
electrons
Discovered the nucleus. Also fired at thin gold leaf.
Atomic Model Today
Atoms are discovered that the nucleus was Most went through the
spheres and each very small and positively gold leaf (mainly empty Electrons don’t have the
element is made charged. He also concluded the space). Small number same energy in shells. We
from different atom was mainly empty space deflected back (they hit have subshells. This
spheres. made up a negative ‘cloud’. a small positive nucleus) explains ionisation trends.

1800 1900 The experimental 2000

Positive proof
1897 J.J.Thomson 1913 Niels Bohr
‘pudding’ When EM radiation is
Discovered a problem with absorbed, electrons
Discovered the
Rutherford’s model. The cloud move between shells.
electron. The atom
- of electrons could collapse into They emit this radiation
wasn’t solid and was
the positive nucleus! He when electrons move
made up of other
proposed electrons were in down to lower energy
particles. The plumb
fixed energy shells. shells.
pudding model was Negative
developed. electrons
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Time of Flight Mass Spectrometer

2. Ionisation
The sample is pushed through a nozzle making
a high pressure jet. A high voltage is passed
through causing the loss of an electron. A
gaseous positively charged sample is
produced. We call this electrospray ionisation.
4. Ion Drift
Particles travel through with a constant speed
and kinetic energy. They drift through and
particles with lower mass/charge (m/z) ratios
travel faster.



1. Vaporisation
The sample is vaporised so it
can travel through the TOF
mass spectrometer.
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3. Acceleration
The positive ions are passed through an
electric field. Particles with lower mass/charge
(m/z) ratio will accelerate quicker.
5. Detection
Ions are detected as electrical current
is made when particle hits the plate.
Particles with lower m/z reach the
detector first as they travel fastest.
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Know your definitions

( Ar) ement R
i c
s s
Ma f an el ass of me The a elati
A tom atom o the m asu ve ve
tive n ch red rage Mo
Rela ass of a on whi 12. on ma lecu
ge m s ca le a ctly ato sca ss o lar
e ra o n e x m le o f a Ma
av ed 12 C is
The s u r f of 12 n w m ss
e n mea atom o C i hic olec (Mr)
wh an s e h t ule
xac he w
tly ma hen
12
. ss o f
an
Relative Isotopic Mass
The mass of an atom of an isotope of an
element measured on scale on which the mass
of an atom of 12C is exactly 12.

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Mass Spectra - Isotopes

The abundance is always shown This spectra shows 2 isotopes of
on this axis. It can be shown as % ONE element. There are –
100 or as a nominal value. If it is in % 75% of isotopes with mass 35
all your isotopes MUST add to 25% of isotopes with mass 37
give 100% (assuming they have a +1 charge)
80 75%

60
% Abundance

From this we can work out the

relative atomic mass! (see next
40 slide)
25%
20
m/z is just the mass of an
0 isotope divided by charge. As
35 36 37 38 most have just a +1 charge this is
Mass/charge OR m/z the same as the isotopic mass.
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Mass Spectra - Isotopes

From this we can work out the
relative atomic mass!

100 Relative atomic mass = () + () Total Abundance

80 75%

60 Relative atomic mass = (7535) + (37) = 35.5 100

% Abundance

40
25%
20 This element is –

0
35 36 37 38
Chlorine (Cl)
Mass/charge OR m/z
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Mass Spectra - Isotopes

From this we can work out the
relative atomic mass!

Isotope m/z Abundance % Relative atomic mass = () + () Total Abundance

70 20.5

72 27.4 Relative atomic mass = (70) + () + ()+ ()+ () 100

73 7.8

74 36.5
The answer is 72.6
75 7.8
Germanium (Ge)
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Mass Spectra - Molecules

The abundance is always shown
on this axis. It can be shown as %
100 or as a nominal value. If it is in %
all your isotopes MUST add to
give 100%
80
Relative Abundance
Peaks show fragments of the
original molecule.
The last peak is the M+ peak OR
the molecular ion peak.
This is the same as the relative
molecular mass of the molecule!

60

40

20 M+

m/z is just the mass of a

0 fragment divided by charge. As
35 40 45 50 most have just a +1 charge this is
Mass/charge OR m/z the same as the fragment mass.
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Electron Configuration
s – has 1 orbital can hold 2 electrons

p – has 3 orbitals can hold 2 × 3 = 6 electrons

Electron shells are split into 4 subshells
d – has 5 orbitals can hold 2 × 5 = 10 electrons

f – has 7 orbitals can hold 2 × 7 = 14 electrons

Shell Number Sub-shells Number of electrons

1 1s 2
2 2s, 2p 2 + (3×2) = 8
3 3s, 3p, 3d 2 + (3×2) + (5×2) = 18

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Electron Configuration - Atoms

This tells you the shell 4d

1s
number 4p
2 This tells you the sub-shell
↑↓ ↑ ↑
↑↓ ↑↓ ↑↓
↑ ↑ 3d ↑↓
4s
This tells you the number 3p
of electrons

Energy
↑↓
3s
We fill orbitals singly ↑↓ ↑↓ ↑↓
first then pair up. 2p
The electron configuration for
Iron is. This due to electron ↑↓
repulsion. 2s
↑↓
1s
1s 2s 2p 3s 3p 3d 4s
2 2 6 2 6 6 2 56

Check! – Use the small numbers –

they should add to give 26
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We fill from the lowest energy
level upwards.
Fe 26
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Electron Configuration – Ions

4d
With ions you just add or remove electrons from the highest 4p
energy level first.
3d ↑↓
Transition metals behave differently (see next slide) 4s
↑↓ ↑↓ ↑
↑↓↓
3p

Energy
↑↓
The electron configuration for Loses 2 electrons, 2 3s
Ca2+ from 4s ↑↓ ↑↓ ↑↓
2p

1s2 2s2 2p6 3s2 3p6 4s2 ↑↓

↑↓
2s
1s
Lose from 4s
Check! – Use the small numbers –
they should add to give 20 – 2 = 18

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Electron Configuration – Transition metals

Chromium and Copper behave differently. 4d
An electron from the 4s orbital moves into the 3d orbital to create 4p
a more stable half full or full 3d sub-shell respectively. ↑↓
↑ ↑ ↑ ↑ ↑ 3d ↑↓
E.g. Cr is 1s2,2s2,2p6,3s2,3p6,3d5,4s1 NOT 1s2,2s2,2p6,3s2,3p6,3d4,4s2 ↑↓ ↑↓ ↑↓ 4s
3p

Energy
↑↓
Transition metal ions behave differently too 3s
↑↓ ↑↓ ↑↓
2p
The electron configuration for Loses 3 electrons, 2
Fe3+ from 4s & 1 from 3d ↑↓
2s
↑↓
1s
1s2 2s2 2p6 3s2 3p6 3d56 4s2
Lose from 4s first then 3d!
Check! – Use the small numbers –
they should add to give 26 – 3 = 23
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+
Ionisation
Ionisation energy is the minimum amount of energy required to remove 1 mole of electrons from 1 mole of
atoms in the gaseous state

Na(g)  Na+(g) +e- 1st IE energy = + 495.8kJmol-1

Always include Ionisation requires energy so they are always an
state symbols (g) + +
endothermic processes and have a positive value

Shielding Atomic Size

Nuclear Charge
The more electrons shells The bigger the atom the further
The more protons in the nucleus
between the positive nucleus and away the outer electrons are from
the bigger the attraction between
negative electron that is being the nucleus. The attractive force
nucleus and outer electrons. This
removed the less energy is between nucleus and outer
means more energy required to
required. There is a weaker electrons reduces – easier to
remove the electron.
attraction. remove electrons.
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+
Successive Ionisation
The removal of more than 1 electron from the same atom is called successive ionisation

Mg+(g)  Mg2+(g) +e- 2nd IE energy = + 1450kJmol-1

General increase in energy as Successive ionisation - Mg
removing an electron from an
6
increasingly more positive ion.

Log Ionisation energy kJmol-1

5

3p 4
Energy

↑↓ 3 We know this is
3s 2 Mg as we are
↑↓ ↑↓ ↑↓ removing 12
2p 1

Jump in energy as removing electrons.

0
↑↓ 1 2 3 4 5 6 7 8 9 10 11 12
2s electrons from shell closer to
↑↓ nucleus Number of electrons removed
1s
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+
1 Ionisation Trends - Groups
st

Ionisation energy decreases as we go down a group

The atomic radius increases as we go down the 1st ionisation energy in Group 2
group. Outer electrons further from the
nucleus. Attractive force is weaker. Energy
1000
required to remove an electron decreases.
900

1st Ionisation energy kJmol-1

800
Shielding increases as we go down the group.
700
More shells between nucleus and outer shell. 600
Attractive force is weaker. Energy required to 500
remove an electron decreases. 400
300
This data provides strong evidence for shells in 200
atoms and proves Niels Bohr’s model of the 100
atom is correct. BUT it didn’t explain data shown 0
Be Mg Ca Sr Ba
going across a period. (See next slides) Group 2 elements

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+
1 Ionisation Trends – Periods
st

Ionisation energy increases as we go across a period

As we go across the period there 1st ionisation energies in period 3

is an increasing number of
protons in the nucleus. This 1600
increases the nuclear attraction. 1400

1st Ionisation energy kJmol-1

1200
1000
Shielding is similar and
distance from nucleus 800

marginally decreases. 600

400
200
More energy required to 0
Na Mg Al Si P S Cl Ar
remove an outer electron.
Ionisation energy increases. Period 3 elements

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+
1 Ionisation Trends – Periods
st

A decrease at Aluminium is evidence for atoms having sub-shells

The outer most electron in Aluminium 1st ionisation energies in period 3

sits in a higher energy sub-shell slightly
further from the nucleus than the outer 1600

electron in Magnesium. 1400

1st Ionisation energy kJmol-1

1200
The atomic model Niels 1000
Mg – 1s2,2s2,2p6,3s2
Bohr came up with didn’t 800
Al - 1s2,2s2,2p6,3s2,3p1
explain sub-shells. 600
400
200
Magnesium Aluminium 0
has it’s outer has it’s outer
Na Mg Al Si P S Cl Ar

electron in 3s electron in 3p Period 3 elements

sub-shell sub-shell
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+
1 Ionisation Trends – Periods
st

A decrease at Sulfur is evidence for electron repulsion in an orbital

Phosphorous and Sulfur both have
outer electrons in the 3p orbital so
the shielding is the same.
Electron Energy
Removing an electron from
Sulfur involves taking it from 1st ionisation energies in period 3
an orbital with 2 electrons in.
1600
1400

1st Ionisation energy kJmol-1

Diagram for Sulfur
1200
1000
↑↓ ↑ ↑
3p 800
Energy

↑↓ 600
3s 400
Electrons
↑↓repel ↑↓each↑↓other 200
so less energy is needed2p to
remove an electron ↑ ↑ ↑ 0
↑↓ from an
Na Mg Al Si P S Cl Ar
3p
2s
orbital with 2 in than a one Period 3 elements
↑↓ ↑↓
with 1 in like
1s Phosphorus. 3s
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