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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:
Particle

Relativemass

Relative charge

proton

+1

neutron

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

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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.
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Isotopes of chlorine
About 75% of naturally-occurring chlorine is chlorine-35 (35Cl)
and 25% is chlorine-37 (37Cl).

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17 protons

17 protons

18 neutrons

20 neutrons

17 electrons

17 electrons

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

Protons

Neutrons

12

13

14

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.

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Whats the number?

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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:

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carbon-14 dating

detecting illegal drugs

forensic science

space exploration.
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Mass spectrometry

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Parts of the mass spectrometer

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Process of mass spectrometry

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Mass spectra of monatomic elements

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Mass spectra of diatomic elements

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Process of mass spectrometry

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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.
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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:
abundance (%)

100
B (80%)

11

80
60
40

10

B (20%)

20
0
0

6
m/z

10

12

How can this be used to calculate the Ar of boron?


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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
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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
of each isotope

24 79.0
25 10.0
26 11.0

2. Add these values,


and divide by 100

(1896 + 250 + 286) / 100


Ar of Mg = 24.3

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Ar calculations

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Glossary

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Whats the keyword?

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Multiple-choice quiz

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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.
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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 Planks 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.
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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.
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Ionization energy definitions

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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
5
electrons are removed.
4
3
2

1 st
2 nd
3 rd
4 th
5 th
6 th
7 th
8 th
9 th
10
th
11
th
12
th

ionization energy

Evidence for energy levels

Large jumps in the ionization


energy reveal where electrons
are being removed from the
next principal energy level,
such as between the 2nd and
3rd, and 10th and 11th ionization
energies for magnesium.

electron removed
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More evidence for energy levels

first ionization energy


(kJ mol-1)

The first ionization energies of group 2 elements also show


evidence for the existence of different principal energy levels.
Even though the nuclear
charge increases down the
group, the first ionization
energy decreases.

900
800
700
600
500
400
Be
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Mg

Ca
Sr
element

This means electrons are


being removed from
successively higher
energy levels, which lie
further from the nucleus
and are less attracted to
Ba
the nucleus.
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Trends in first ionization energies

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Energy levels

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first ionization energy


(kJ mol-1)

Evidence for sub-levels


1600
1400
1200

The first ionization


energies for the elements
in period 3 show a
general increase.

1000

However, aluminiums
800
value is below that of
magnesium. This suggests
600
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.
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The sub-levels
There are four sub-levels,
labelled in order of
increasing energy: s, p, d
and f. Each holds a
different number of
electrons.
Each principal
energy level
contains a
different
number of
sub-levels.

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sub-level max no. electrons


s

10

14

principal energy
level, n

max no.
electrons

sub-levels

1s

2s, 2p

3s, 3p, 3d

18

4s, 4p, 4d, 4f

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Levels and sub-levels

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Blocks of the periodic table

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Order of sub-levels

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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.
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Writing electron configuration

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Electron configuration: true or false?

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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


4s is filled before 3d

1s22s22p63s23p64s23d3

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Electronic configuration: atoms

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Electron configuration of ions


When writing the electron
configuration of ions, it is
important to add or subtract the
appropriate number of electrons.
For non-transition metals, the sublevels are then filled as for atoms.

For negative ions


add electrons.
For positive ions
remove electrons.

Example: what is the electron structure of O2-?


1. Count number of electrons in atom

2. Add or remove electrons due to charge

8 + 2 = 10

3. Fill sub-levels as for uncharged atom

1s22s22p6

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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
in atom

28

2. Fill sub-levels, remembering


4s is filled before 3d

1s22s22p63s23p64s23d8

3. Count number of electrons


to be removed

4. Remove electrons starting


with 4s

1s22s22p63s23p63d8

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Electron configuration: ions

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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

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Shapes of electron orbitals

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

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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.
Hunds 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.
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Evidence for Hunds rule

first ionization energy


(KJ mol-1)

The first ionization energies for the elements in period 3 show


a general increase.
1600
1400
1200
1000
800
600

However, sulfurs value


is below that of
phosphorus. As the
highest energy
electrons of both are in
the 3p sub-level this is
evidence for Hunds
rule.

400
Na Mg Al Si P S Cl Ar
element

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Evidence for Hunds 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
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sulfur
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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.
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Creating spin diagrams

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Glossary

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Whats the keyword?

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Energy levels and electrons

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Multiple-choice quiz

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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.
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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
between two identical atoms in
a single covalent bond.

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covalent
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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.
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Trends in atomic radius in period 3

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Trends in atomic radius in period 3


Atomic
Element
radius (nm)
Na

0.190

Mg

0.145

Al

0.118

Si

0.111

0.098

0.088

Cl

0.079

Ar

0.071

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The atomic radius of the elements


across period 3 decreases.
This might seem counterintuitive, because as the
numbers of sub-atomic particles
increase, the radius might be
expected to also increase.
However, more than 99% of the
atom is empty space the
nucleus and electrons themselves
occupy a tiny volume of the atom.

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Increase in proton number


The number of protons in the nucleus of the atoms
increases across period 3.
proton
number

Element

Na

11

12

Mg

13

Al

14

Si

15

16

17

Cl

Ar

18

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

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What is shielding?

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Explaining atomic radius in period 3


Atomic
Proton
Element
radius
number
(nm)
Na

11

0.190

Mg

12

0.145

Al

13

0.118

Si

14

0.111

15

0.098

16

0.088

Cl

17

0.079

Ar

18

0.071

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Proton number increases


across period 3, but
shielding remains
approximately constant.
This causes an increase
in effective nuclear
charge, leading to a
greater attraction
between the nucleus and
the outermost electrons.
This pulls these electrons
closer to the nucleus and
results in a smaller radius.
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Atomic radius in period 3

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Atomic radius: true or false?

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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) + eThe 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.
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Plot of the first ionization energies

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General trend in first ionization energy


1600
ionization energy
(kJ mol-1)

There is a general
increase in the first
ionization energies
across period 3.

1400
1200
1000
800

Across period 3, the


600
proton number
400
increases but the
Na Mg Al Si P S Cl Ar
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.
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Trend in first ionization energy: exceptions

ionization
energy (kJ mol-1)

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
1400
1200
1000
800
600
400
Na Mg Al

lower
ionization
energies
than
expected
Si

Cl

Ar

element
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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

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aluminium

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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

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sulfur

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Ionization energy in period 3

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Ionization energy in period 3

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Plot of the melting and boiling points

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Na, Mg and Al: melting and boiling points


The melting and boiling points increase for the three metallic
elements from sodium to aluminium.

temperature (K)

3000
2500
2000
1500
1000
500
0
Na

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boiling point
melting point
Mg
element

Al

This is because the


strength of the
metallic bonds
increases. More
energy is needed to
break the stronger
metallic bonds, so
melting and boiling
points are higher.

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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
ions 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.
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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.

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Period 3 non-metals
The melting and boiling points of phosphorus, sulfur and
chlorine are much lower than those of silicon.
temperature (K)

This is because
they have a
simple molecular
structure with
weak van der
Waals forces
holding the
molecules together.

3500
3000
2500
2000
1500
1000
500
0
Na

Mg

Al

Si
P
element

Cl

Breaking these forces of attraction requires much less


energy than breaking covalent bonds.
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Ar

Period 3 non-metals: structure

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Melting points in period 3

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Melting points in period 3

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Glossary

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Whats the keyword?

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Multiple-choice quiz

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