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Electronic structure of atoms and ions

Only electrons are involved in chemical reactions (breaking and making bonds) we dont
turn atoms into different atoms, so nuclei remain unchanged. It is therefore the
arrangement of the electrons in their shells that gives an atom or ion its chemical
properties.
Bohrs model of electronic structure
Bohr's model stated that electrons only have fixed amounts of energy, which means they
are confined to specific energy levels, often called shells.
They can move from one shell to another, but not exist anywhere outside a shell. When
they move from one shell to another, they have to absorb or emit the difference in energy
between the shells. The further from the nucleus a shell is, the higher its energy is.
Bohr also proposed that each shell has a maximum number of electrons it can contain.
The contributions of Quantum Mechanics
The currently accepted model of the atom makes use of quantum mechanics to build on
Bohrs model, adding further detail and sophistication to allow additional phenomena to be
explained:

Electrons occupy defined regions of space called orbitals. An orbital can only contain 0,
1 or 2 electrons, never more. Along with being negatively charged, electrons have a
momentum-related property called spin. We denote the spin of the first electron in an
orbital as up (shown as ) and a second electron in an orbital then has down spin ().
To share an orbital, electrons must have opposite spin. Definition: An orbital is a region
of space that can hold up to two electrons, each having opposite spins.

There are different types of orbitals, with specific shapes (they are actually fuzzy shapes
but it is easier to draw the edge of the space where there is a 90% probability of finding
the electron).
An s-orbital has spherical shape, drawn in 2-D as:

A p-orbital has a lobed-shape, drawn in 2-D:

There are also d- and f-orbitals (the shapes get weirder - Google them!)

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Orbitals always come in sets - called subshells. A subshell is a set of orbitals of the
same type:
s-subshell = one s-orbital (so it can contain up to 2 electrons)
p-subshell = three p-orbitals (so can contain up to 6 electrons)
These are arranged along the x,y and z axes (px, py and pz orbitals, so their
orientation in space is at 90 to one another)
d-subshell = five d-orbitals (so can contain up to 10 electrons)
f-subshell = seven f-orbitals (so can contain up to 14 electrons)

Each shell has a number the principle quantum number, n. The innermost shell is
n=1, and so on outwards. Shells consist of a set of subshells.
Shell n=1 is composed of just an s-subshell, labeled 1s
so n=1 can contain up to 2 electrons
Shell n=2 is composed of an s-subshell and a p-subshell labeled 2s and 2p
so n=2 can contain 2+6 = 8 electrons in total
Shell n=3 is composed of the 3s subshell, the 3p-subshell and the 3d-subshell
so n=3 can contain up to 2+6+10 = 18 electrons
n=4 is composed of the 4s-subshell, 4p subshell, 4d subshell and and 4f subshells
so n=4 can actually contain 2+6+10+14 = 32 electrons
and so on

Filling Rules:
We know how many electrons an atom has, from the atomic number. We now need rules to
tell us how these electrons are arranged in the shells, subshells and orbitals in the ground
state (the lowest atomic energy, when none of the electrons have been excited to higher
energy levels, which is the normal state for the atom)
RULE 1) An electron will go into the lowest available energy subshell. Within a shell, the ssubshell is lower in energy than the p-subshell, and p-subshell is lower in energy than the
d-subshell etc.
What determines the energy of a subshell is how far away from the nucleus (on average)
the electrons are in that subshell the nearer to the nucleus, the lower the energy of the
subshell. There are some surprises because of the shapes of the orbitals being different
e.g. the electrons in the 4s subshell are on average nearer the nucleus than those in 3d,
and so lower in energy than 3d. Which means the 4s subshell will fill before the 3d.

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An energy level diagram helps show this:


4d
5s

4p

3d

4s
3p
3s

energy

2p
2s
1s
n=1

n=2

n=3

n=4

n=5

This means the order of filling goes: 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d,
Remembering filling order:

RULE 2) All the orbitals in a subshell be occupied by a single electron before any of them
can have a second electron.
Writing electron arrangements
You may be asked to write the electron arrangement in subshell notation, or using electronin-box diagrams.
Atom

electrons

subshell notation

electrons-in-boxes

H
He
Li
O
K

1
2
3
8
19

1s1
1s2
1s2 2s1
1s2 2s2 2p4
1s2 2s2 2p6 3s2 3p6 4s1

1s

2s

2p

3s

3p

3d

4s

Its pretty time-consuming filling in the full notation, so sometimes we use the symbol for the
Noble Gas at the end of the previous period to represent the filled shells e.g.
K
1s2 2s2 2p6 3s2 3p6 4s1 = [Ar] 4s1
Ca
1s2 2s2 2p6 3s2 3p6 4s2 = [Ar] 4s2
Sc
1s2 2s2 2p6 3s2 3p6 3d1 4s2 = [Ar] 3d1 4s2 (we are now filling an INNER shell)
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N.B. the subshells are normally written in shell order, not in filling order, so 3d is written
before 4s, as seen in Sc = 1s2 2s2 2p6 3s2 3p6 3d1 4s2, but the 3d subshell need not be
written when it has no electrons in it, so Ca = 1s2 2s2 2p6 3s2 3p6 4s2 rather than 1s2 2s2 2p6
3s2 3p6 3d0 4s2.
Blocks in the periodic table
Elements belong to the s-block, p-block, d-block or f-block corresponding to their highest
energy subshell containing electrons:

Group 1 and Group 2, and Helium are the s-block elements


In between Group 2 and Group 3 are the d-block elements
Groups 3-8 (except He) are the p-block elements
The f-block elements are typically shown at the bottom of the table

Electron arrangements for ions


Starting with the electron arrangement for the corresponding atom, either add electrons (for
a negatively charged ion) or remove electrons (for positively charged ions) from the highest
energy subshell according to the charge on the ion.
e.g.

Ca = 1s2 2s2 2p6 3s2 3p6 4s2

Ca2+ = 1s2 2s2 2p6 3s2 3p6

It is important to realize that 4s and 3d are sufficiently close in energy that putting electrons
into 3d swaps the relative energies of 3d and 4s, so electrons are removed from 4s before
3d when forming ions of the d-block elements.
e.g.

Fe = 1s2 2s2 2p6 3s2 3p6 3d6 4s2

Fe3+ = 1s2 2s2 2p6 3s2 3p6 3d5

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Check your understanding:


1.
Show electron arrangements in
i) Kr
ii) Fiii) N3iv) K+
v) S2vi) Li+
Ionisation Energies
Evidence for the arrangement of electrons in shells with different energies comes from
experiments in which electrons are progressively removed from atoms. The process of
removing an electron is referred to as ionisation, and the energy needed to remove the
electron is called the ionisation energy. An atom has as many ionisation energies as it
has electrons.
Definition: The first ionisation energy of an element is the energy required to remove one
electron from each atom in a mole of atoms of an element in the gaseous state, to form one
mole of gaseous 1+ ions.
The symbol is Hi, and we add a subscript number to show which ionisation energy we are
referring to:
Hi1 = 1st ionization energy etc.
We use an equation to show precisely what we mean:
Ca(g) Ca+(g) + e-

Hi1 = +590 kJ mol-1

Similarly, the second ionization energy of calcium (energy to remove not two electrons, but
to remove one electron from a calcium ion having already had one removed) can be written
as:
Ca+(g) Ca2+(g) + eHi2 = +1150 kJ mol-1
(Note that these equations ALWAYS only have one electron in them)
Check your understanding:
2.
i) Write down an equation to show the third ionization energy of aluminium
Successive Ionisation Energies
We could keep removing electrons until only the nucleus is left this would give us the
successive ionisation energies of the element. We can use these successive ionisation
energies to identify what shells an unknown atom has, and how many electrons occupy
each shell.
Definition: The successive ionisation energies of an element are the energies required to
remove the electrons successively from each atom in a mole of gaseous atoms of an
element, to form one mole of increasingly positively charged gaseous ions.

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For example, consider the successive ionisation energies of sodium (ionisation energies
have been determined for most atoms, using emission spectra and electron bombardment
of gaseous atoms): Na = 1s2 2s2 2p6 3s1
Ionisation
1st
2nd
3rd
4th
5th
6th
7th
8th
9th
10th
11th

Electron Arrangement
after ionisation
1s2 2s2 2p6
1s2 2s2 2p5
1s2 2s2 2p4
1s2 2s2 2p3
1s2 2s2 2p2
1s2 2s2 2p1
1s2 2s2
1s2 2s1
1s2
1s1
-

Electron
removed*
3s1
2p6
2p5
2p4
2p3
2p2
2p1
2s2
2s1
1s2
1s1

Ionisation
Energy (kJmol-1)
510
4,560
6,940
9,540
13,400
16,600
20,100
25,500
28,900
141,000
158,700

*Get into the habit of working out the electron arrangement for the
atom first, then writing which electron has been removed with each
ionisation

Examining this data we can see


The energy required to remove electrons gets progressively greater
There are two steps in energy, after the 1st and 9th ionisation
The successive ionization energies reflect the arrangement of electrons in shells,
supporting the Bohr model for sodium. The large steps in ionization energy correspond to
starting to remove electrons from a principle quantum shell closer to the nucleus.
Using successive ionisation data, we can therefore determine which Group an element
belongs to by noting the number of electrons that can be removed before the first large step
in ionisation energy. If all the successive ionisations are given, we can also determine
which period an element is in, by noting the number of steps in ionisation energy, each
corresponding to starting to remove electrons from a new shell closer to the nucleus. Note:
you may be presented with the first n successive ionisation energies rather than the full
set. Dont assume the ionisation energy you are given is for the 1s1 electron!

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Application
The first six successive ionisation energies of an element in period 3 (in kJmol -1) are: 578,
1817, 2745, 11577, 14842, 18379.
i) Interpret this data in terms of the electron arrangement of this element, and hence
identify the element
ii) sketch a graph showing the full set of successive ionisation energies of this
element
i) There is a step in the ionisation energies after the
3rd ionisation, so there are 3 electrons in the outer
shell, and this element is in Group 3. Since it is in
Period 3, the element is aluminium.
ii) Once the outer shell electrons have been
removed, aluminium has 8 electrons to remove from
the n=2 shell, then 2 from the n=1 shell, each
ionisation requiring more energy than the last. There
will therefore be another step in ionisation energy
after the 11th ionisation, corresponding to starting to
remove electrons from the n=1 shell.

Factors that affect ionisation energies


The nuclear charge the more protons in the nucleus, the more strongly they will attract
the electron being being removed.
Distance from nucleus the further away the electron to be removed is from nucleus,
the weaker the attraction of the nucleus will be.
Shielding filled inner shells of electrons shield the electron to be removed, reducing the
attraction of between it and the nucleus.
We need to consider all three of these factors when we explain how the attraction between
electrons and the nucleus varies, and hence and why ionisation energies vary:
Application
i) Explain why there is a large difference between the first and second ionisation energies
of sodium:
Sodium has electron arrangement 1s2 2s2 2p6 3s1. The nuclear charge remains constant,
but the first electron removed therefore comes from the n=3 shell and is therefore
significantly further from the nucleus than the second electron to be removed. There are
also two filled shells (n=1 and n=2) shielding it from the nuclear charge, while the second
electron to be removed experiences shielding only from the n=1 shell. As a result the first
electron to be removed experiences much weaker attraction from the nucleus, and
therefore takes much less energy to remove.

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ii) Explain why there is an increasing trend in the 2rd to 9th ionisation energies of sodium.
Sodium has electron arrangement 1s2 2s2 2p6 3s1. During the 2rd to 9th ionisations,
electrons are being removed from the n=2 principle quantum shell and therefore experience
the same shielding from the filled n=1 shell. They also experience the same nuclear
charge. However, as electrons are removed from the n=2 shell the repulsion between the
remaining electrons in the shell decreases, and the shell contracts, becoming closer to the
nucleus. This means that the attraction between the electron being removed and the
nucleus increases, and therefore the energy required to remove the electron increases.
Check your understanding
3.
The first six ionisation energies of an element in period 3 are 787, 1577, 3232, 4356,
16091, 19805 kJmol-1.
i)
Identify the element, explaining your reasoning.
ii)
Predict the value of the seventh ionisation energy, explaining your reasoning.

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Answers to 'Check your understanding' questions


1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6
1s2 2s2 2p6
1s2 2s2 2p6
1s2 2s2 2p6 3s2 3p6
1s2 2s2 2p6 3s2 3p6
1s2

1.

i)
ii)
iii)
iv)
v)
vi)

Kr
FN3K+
S2Li+

2.

i)

Al2+(g) Al3+(g) + e-

3.

i) There is a step in ionisation energy after the 4th ionisation, so the element has four
outer shell electrons. It is therefore in group 4. The element in period 3 group 4 is
silicon.

this is denoted Hi3

ii) Silicon is 3p2 3s2 2p6 2s2 1s2, so the 7th ionisation is removal of the 2p4 electron. It
will therefore have an ionisation energy similar to, and a little greater than, the 6th
ionisation energy which corresponded to removal of the 2p5 electron. This is
because the 2p4 electron experiences the same shielding and nuclear charge, but is
slightly closer to the nucleus and therefore more strongly attracted due to the
decrease in repulsion between electrons in n=2 with removal of the 2p 5 electron. It is
therefore reasonable to suggest that the 7th ionisation energy will be in the region of
23000 kJmol-1 (accept any value from 20000 to 26000 kJmol-1).

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