1

1.1 Atomic structure

The Structure of the Atom
Mass Spectrometry
Electronic Structure
Ionisation Energies

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THE STRUCTURE OF THE ATOM

a) Protons, neutrons and electrons

Atoms are made up of three fundamental particles: protons, neutrons and

electrons.

Protons and neutrons are found in the nucleus and are collectively called
nucleons. Electrons orbit the nucleus in a similar way to that in which planets orbit
a sun. In between the electrons and nucleus there is nothing (empty space).
The nucleus is very small; if an atom were the size of a football pitch, the nucleus
would be the size of a drawing pin.

The basic properties of these three particles can be summarized in the following
table:

Particle Charge Mass

Proton +1 unit Approx 1 unit

Neutron No charge Approx 1 unit
Electron -1 unit Approx 1/1840 units (very small)

1 unit of charge is 1.602 x 10-19 coulombs. A proton is given a charge of +1 and an

electron a charge of -1. All charges are measured in these units.

1 unit of mass is 1.661 x 10 -27 kg. This is also not a convenient number, so we use
“atomic mass units”.
Since the mass of protons and neutrons varies slightly depending on the nucleus,
then in order to define an “atomic mass unit” we need to choose one nucleus as a
standard. For this purpose 126C , or “carbon-12”, was chosen because its mass per
nucleon
(1.661 x 10 –27 kg) is around average, which means all the other nuclei have masses
close to whole numbers. An atomic mass unit is thus defined as 1/12 th of the
mass of one atom of carbon-12. Everything else is measured relative to this
quantity.

b) Atomic numbers, mass numbers and isotopes

An atom is named after the number of protons in its nucleus. If the nucleus of an
atom has 1 proton, it is hydrogen; if it has two protons, it is helium; if it has 3, it is
lithium etc. The number of protons in the nucleus of an atom is called the atomic
number. It has the symbol Z.

The atomic number is the number of protons in the nucleus of an atom

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Not all atoms of the same element have equal numbers of neutrons; this may vary
slightly. The sum of the number of protons and neutrons in the nucleus of an atom
is called its mass number. It is represented by the symbol A.

The mass number is the sum of the number of protons and neutrons in the nucleus of an atom

The nucleus of an atom can thus be completely described by its mass number and
its atomic number. It is generally represented as follows:
A
ZE

Eg. 94Be, 126C, 2412Mg

Atoms with the same atomic number but with different mass numbers (ie different
numbers of neutrons) are called isotopes.

Isotopes are atoms with the same atomic number but with different mass numbers

Eg magnesium (atomic number 12) has 3 naturally occurring isotopes:

24
12 Mg: 12 protons, 12 neutrons
25
12 Mg: 12 protons, 13 neutrons
26
12 Mg: 12 protons, 14 neutrons

In a neutral atom, the number of protons and electrons are the same. However,
many elements do not exist as neutral atoms, but exist as ions. Ions are species in
which the proton and electron numbers are not the same, and hence have an
overall positive or negative charge. The number of electrons in a species can be
deduced from its charge:

Eg
24
12 Mg2+: 12p, 12n, 10e
24
12 Mg+: 12p, 12n, 11e
24
12 Mg 12p, 12n, 12e
24
12 Mg-: 12p, 12n, 13e

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c) Relative atomic mass

The mass of an atom is measured in atomic mass units, where one unit is 12 th of
the mass of one atom of carbon-12.

The relative isotopic mass of an isotope is the ratio of the mass of one atom of
that isotope to 1/12th of the mass of one atom of carbon-12.

It is usually very close to a whole number ratio:

Isotope Mass number Relative isotopic mass

1
1H 1 1.006
4
2He 4 4.003
9
4Be 9 9.012
27
Al
13 27 26.919
59
Co
27 59 58.933

The masses of protons and neutrons vary slightly from isotope to isotope, so the
relative isotopic mass is not exactly a whole number.

The relative atomic mass of an atom is the ratio of the average mass of one atom of that
element to 1/12th of the mass of one atom of carbon-12.

The RAM is the average mass of all the isotopes, and is often not close to a whole
number:

Element Common mass numbers Relative atomic mass

Mg 24, 25, 26 24.32

Cl 35, 37 35.45
Br 79, 81 79.91
Ba 134, 135, 136, 137, 138 137.33

Some elements and compounds exist as molecules; these also have a

characteristic mass:

The relative molecular mass of a molecule is the ratio of the average mass of that
molecule to 1/12th of the mass of an atom of carbon-12.

The relative molecular mass of a molecule is the sum of the relative atomic masses
of its constituent atoms.

Eg The relative molecular mass of CO2 is 12.0 + 16.0 + 16.0 = 44.0

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MASS SPECTROMETRY

The mass spectrometer is an instrument used for measuring the masses of atoms
and molecules. It can also be used to measure the relative abundance of different
isotopes and to predict the structure of more complex molecules.

1. How the mass spectrometer works

The workings of the mass spectrometer can be summarized in five stages:

1- Gaseous material released into ionization chamber

2- Particles bombarded with electrons and ionized, mostly to +1 ions

(IONISATION)
A metal wire is heated until it starts emitting high energy electrons. These
electrons hit the particles, knocking more electrons off. Most of the particles are
ionized to +1 ions

3- Ions accelerated to uniform speed by electric field (ACCELERATION)

The positive ions are attracted to the negative plate and accelerate towards it

4- Ions deflected by magnetic field; deflection depends on m/e ratio

(DEFLECTION)
The heavier the particle, the less the deflection

5- Electric current measured as ions land on plate (DETECTION)

The greater the abundance of the isotope, the larger the current

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The degree of deflection depends on the mass and the charge; the greater the
mass, the less the deflection, and the greater the charge, the greater the deflection.
It can be shown that the deflection is inversely proportional to the m/e ratio.

In most cases, however, the charge is +1, so the deflection depends essentially on
the relative mass of the species in the mass spectrometer. If the spectrometer is
calibrated, the masses of all the species can be directly measured.

The greater the number of particles landing at a single point on the detector, the
greater the electric current and the larger the peak. Thus the relative abundance of
different isotopes can be measured.

Since the position at which an ion appears on the detector depends on its mass,
different isotopes appear at different points on the detector. The magnitude of the
peak gives the relative abundance of the isotope.

Thus the relative atomic mass of the element can be calculated from its mass
spectrum.

An example of a simple mass spectrum is shown below:

Mass spectrum of Ne

The peak at 20 is 20Ne+, and the peak at 22 is 22Ne+

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2. Calculating relative atomic masses

The relative atomic mass can be calculated by the formula:

Σ (perentage abundance of each isotope x mass of each isotope)
100

Eg. Using the mass spectrum of neon above:

RAM = (90 x 20 + 10 x 22)/100 = 20.2

All relative atomic masses have been found in this way.

3. Deducing relative molecular masses

It is also possible to put molecules into the mass spectrometer. Because the
conditions inside a mass spectrometer are very extreme, the molecules often break
up into smaller pieces. This is known as fragmentation.

The mass spectrum of a molecule can thus look quite complicated:

Mass spectrum of pentane (C5H12)

Many of these peaks result from fragmentation of the molecule, but the peak with
the largest m/e ratio comes from the unbroken molecular ion, in this case C 5H12+,
and is called the molecular ion peak. The m/e ratio of this peak (72) will be the
relative molecular mass of the molecule.

The relative molecular mass of a molecule is obtained by looking at the peak

in the spectrum with the largest m/e ratio (ie the peak furthest to the right).

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ELECTRONIC STRUCTURE

i) Energy levels

Electrons do not orbit the nucleus randomly; they occupy certain fixed energy
levels. Each atom has its own unique set of energy levels, which are difficult to
calculate but which depend on the number of protons and electrons in the atom.

Energy levels in an atom can be numbered 1,2,3,…. To infinity. 1 is the lowest

energy level (closest to the nucleus) and energy level infinity corresponds to the
energy of an electron which is not attracted to the nucleus at all. The energy levels
thus converge as they approach infinity:

ii) Orbitals and sub-levels

Electrons do not in fact orbit the nucleus in an orderly way. In fact they occupy
areas of space known as orbitals. The exact position of an electron within an
orbital is impossible to imagine; an orbital is simply an area of space in which there
is a high probability of finding an electron.

Orbitals can have a number of different shapes, the most common of which are as
follows:

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s-orbitals: these are spherical.

Every energy level contains one s-orbital.

An s-orbital in the first energy level is a 1s orbital.
An s-orbital in the second energy level is a 2s orbital, etc

p-orbitals: these are shaped like a 3D figure of eight. They exist in groups of three:

Every energy level except the first level contains three p-orbitals. Each p-orbital in
the same energy level has the same energy but different orientations: x, y and z.
A p-orbital in the second energy level is a 2p orbital (2px, 2py, 2pz)
A p-orbital in the third energy level is a 3p orbital (3px, 3py, 3pz), etc

In addition, the third and subsequent energy levels each contain five d-orbitals, the
fourth and subsequent energy levels contain seven f-orbitals and so on. Each type
of orbital has its own characteristic shape.

S, p and d orbitals do not all have the same energy. In any given energy level, s-
orbitals have the lowest energy and the energy of the other orbitals increases in the
order p < d < f etc. Thus each energy level must be divided into a number of
different sub-levels, each of which has a slightly different energy.

The number and type of orbitals in each energy level can thus be summarised as
follows:

Energy level Number and type of orbital

1st sub- 2nd sub- 3rd sub- 4th sub- 5th sub-
level level level level level
1 1 x 1s
2 1 x 2s 3 x 2p
3 1 x 3s 3 x 3p 5 x 3d
4 1 x 4s 3 x 4p 5 x 4d 7 x 4f
5 1 x 5s 3 x 5p 5 x 5d 7 x 5f 9 x 5g

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iii) Shells

Since the different sub-levels have different energies, and the energies of the
different levels get closer together with increasing energy level number, the high
energy sub-levels of some energy levels soon overlap with the low energy sub-
levels of higher energy levels, resulting in a more complex energy level diagram:

Starting with the lowest energy, the orbitals can thus be arranged as follows:

1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f
5d 6p 7s 5f 6d

Many of these sub-levels have similar energy, and can be grouped together.
A collection of sub-levels of similar energy is called a shell.

1s│2s 2p│3s 3p │ 4s 3d 4p │5s 4d 5p│6s 4f 5d 6p

The arrangement of shells and the maximum number of electrons in each can be
summarised as follows:

Shell number Orbitals in shell

1 1 x1s
2 1 x 2s, 3 x 2p
3 1 x 3s, 3 x 3p
4 1 x 4s, 5 x 3d, 3 x 4p
5 1 x 5s, 5 x 4d, 3 x 5p
6 1 x 6s, 7 x 4f, 5 x 5d, 3 x 6p

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iv) Electrons

Electrons repel each other. In a small space such as an orbital, it is impossible to

put more than two electrons.

Since electrons are charged particles, and moving charges create a magnetic field,
it is possible to create a small magnetic attraction between two electrons if they are
spinning in opposite directions in the same orbital. This is the reason two electrons,
and not one, are permitted in the same orbital.

It is thus possible to calculate the maximum possible number of electrons in each

sub-level, and thus in each energy level:

Shell Number of electrons in each sub-level Max. no of electrons

1 2 x 1s 2
2 2 x 2s, 6 x 2p 8
3 2 x 3s, 6 x 3p 8
4 2 x 4s, 10 x 3d, 6 x 4p 18
5 2 x 5s, 10 x 4d, 6 x 5p 18
6 2 x 6s, 14 x 4f, 10 x 5d, 6 x 6p 32

v) Electron arrangement in orbitals

There are three rules which determine the way in which electrons fill the orbitals

1. Aufbau/building principle: electrons always fill the lowest energy orbitals first.

2. Hund's rule: electrons never pair up in the same orbital until all orbitals of the
same energy are singly occupied, and all unpaired electrons have parallel spin.

3. Pauli exclusion principle: only two electrons may occupy the same orbital, and
they must do so with opposite spin.

The arrangement of electrons in an atom is known as its electronic configuration.

It can be represented in two ways:

The arrow and box method represents each orbital as a box and each electron as
an arrow. The direction of spin is shown by the orientation of the arrow.

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The electronic configuration of the first 18 elements using the arrow in box method
is as follows:

1s 2s 2p 3s 3p
H ↑

He ↑↓

Li ↑↓ ↑

Be ↑↓ ↑↓

B ↑↓ ↑↓ ↑

C ↑↓ ↑↓ ↑ ↑

N ↑↓ ↑↓ ↑ ↑ ↑

O ↑↓ ↑↓ ↑↓ ↑ ↑

F ↑↓ ↑↓ ↑↓ ↑↓ ↑

Ne ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

Na ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑

Mg ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

Al ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑

Si ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑

P ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑ ↑

S ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑

Cl ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑

Ar ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

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The orbital method indicates the number of electrons in each orbital with a
superscript written immediately after the orbital.

The electronic configurations of the first eighteen elements can be shown with the
orbital method as follows:

H: 1s1
He: 1s2
Li: 1s22s1
Be: 1s22s2
B: 1s22s22p1
C: 1s22s22p2 or 1s22s22p63s23px13py1
N: 1s22s22p3 or 1s22s22p63s23px13py13pz1
O: 1s22s22p4 or 1s22s22p63s23p23px23py13pz1
F: 1s22s22p5
Ne: 1s22s22p6
Na: 1s22s22p63s1
Mg: 1s22s22p63s2
Al: 1s22s22p63s23p1
Si: 1s22s22p63s23p2 or 1s22s22p63s23px13py1
P: 1s22s22p63s23p3 or 1s22s22p63s23px13py13pz1
S: 1s22s22p63s23p4 or 1s22s22p63s23px23py13pz1
Cl: 1s22s22p63s23p5
Ar: 1s22s22p63s23p6

A shorthand form is often used for both the above methods. Full shells are not
written in full but represented by the symbol of the element to which they
correspond, written in square brackets.

Eg. 1s22s22p6 is represented as [Ne] and 1s22s22p63s23p6 is represented as [Ar].

The shorthand electronic configuration of the elements with atomic numbers 18 to

36 can be written as follows:

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4s 3d 4p
K [Ar] ↑

Ca [Ar] ↑↓

Sc [Ar] ↑↓ ↑

Ti [Ar] ↑↓ ↑ ↑

V [Ar] ↑↓ ↑ ↑ ↑

Cr [Ar] ↑ ↑ ↑ ↑ ↑ ↑

Mn [Ar] ↑↓ ↑ ↑ ↑ ↑ ↑

Fe [Ar] ↑↓ ↑↓ ↑ ↑ ↑ ↑

Co [Ar] ↑↓ ↑↓ ↑↓ ↑ ↑ ↑

Ni [Ar] ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑

Cu [Ar] ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

Zn [Ar] ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

Ga [Ar] ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑

Ge [Ar] ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑

As [Ar] ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑ ↑

Se [Ar] ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑

Br [Ar] ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑

Kr [Ar] ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

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Note the unusual structures of chromium and copper.

The difference in energy between the 3d and 4s electrons is very small, and in
chromium the energy required to promote and electron from 4s to 3d is recovered in
the reduced repulsion which results from the fact that they are no longer paired.
Thus the 4s13d5 structure in Cr is preferred.
In copper, the 3d orbitals are actually lower in energy than the 4s orbital, so the
4s13d10 structure in Cu is preferred.

v) Electron arrangement in ions

The electronic configuration of ions can be deduced by simply adding or removing

the appropriate number of electrons. The order in which electrons are to be
removed can be deduced from the following rules:

- remove outer shell electrons first

- remove p-electrons first, then s-electrons and then d-electrons
- remove paired electrons before unpaired electrons in the same sub-level

vi) Effect of electronic configuration on chemical properties

The chemical properties of an atom depend on the strength of the attraction

between the outer electrons and the nucleus. These in turn depend on the number
of protons and on the electronic configuration, and so it follows that these two
factors are instrumental in determining the chemical properties of an atom.

This is in contrast with the neutron number however, which has no effect on the
chemical properties of an atom. Neutrons have no charge and hence exert no
attractive force on the nucleus.

Isotopes, therefore, tend to have very similar chemical properties since they
have the same atomic number and the same electronic configuration. They
differ only in number of neutrons, which do not directly influence the
chemical properties of an element.

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IONISATION ENERGIES

i) First ionisation energy

The first ionisation energy of an element is the energy required to remove one electron
from each of a mole of free gaseous atoms of that element.

It can also be described as the energy change per mole for the process:
M(g)  M+(g) + e

The amount of energy required to remove an electron from an atom depends on the
number of protons in the nucleus of the atom and on the electronic configuration of
that atom.

The first ionisation energies of the first 20 elements in the periodic table is shown
below:

Variation of first ionisation energy with atomic

number for the first twenty elements

2500
first ionisation energy (kJ

2000
per mole)

1500

1000

500

0
0 5 10 15 20
atomic number

There are various trends in this graph which can be explained by reference to the
proton number and electronic configuration of the various elements. A number of
factors must be considered:

- Energy is required to remove electrons from atoms in order to overcome their

attraction to the nucleus. The greater the number of protons, the greater the
attraction of the electrons to the nucleus and the harder it is to remove the
electrons. The number of protons in the nucleus is known as the nuclear charge.

- The effect of this nuclear charge, however, is cancelled out to some extent by the
other electrons in the atom. Each inner shell and inner sub-shell electron effectively
cancels out one unit of charge from the nucleus. This is known as shielding.
- The outermost electrons in the atom thus only feel the residual positive charge
after all inner shell and inner sub-shell electrons have cancelled out much of the

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nuclear charge. This residual positive charge is known as the effective nuclear
charge.

- Electrons repel each other, particularly when they are in the same orbital. The
degree of repulsion between the outermost electrons affects the ease with which
electrons can be moved.

When considering trends in ionisation energies, it is thus necessary to consider 4

factors:

- nuclear charge

- shielding

- effective nuclear charge

- electron repulsion

The trends in first ionisation energies amongst elements in the periodic table can be
explained on the basis of variations in one of the four above factors.

Trend across period 1

Compare the first ionisation energies of H and He. Neither have inner shells, so
there is no shielding. He has two protons in the nucleus; H only has one. Therefore
the helium electrons are more strongly attracted to the nucleus and hence more
difficult to remove.

The first ionisation energy of He is thus higher than that of H.

Since H and He are the only atoms whose outer electrons are not shielded from the
nucleus, it follows that He has the highest first ionisation energy of all the elements.
All elements (except H) have outer electrons which are shielded to some extent
from the nucleus and thus are easier to remove.
So Helium has the highest first ionisation energy of all the elements.

Trends across period 2

Compare now the first ionisation energies of He (1s 2) and Li (1s22s1). Li has an
extra proton in the nucleus (3) but two inner-shell electrons. These inner-shell
electrons cancel out the charge of two of the protons, reducing the effective nuclear
charge on the 2s electron to +1. This is lower than the effective nuclear charge on
the He 1s electrons, +2, and so the electrons are less strongly held and easier to
remove.

The first ionisation energy of Li is thus lower than that of He.

Compare the first ionisation energies of Li (1s 22s1) and Be (1s22s2). Be has one
more proton in the nucleus than Li, and no extra inner-shell electrons, so the

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effective nuclear charge on Be is higher and the Be electrons are more strongly
attracted to the nucleus.

The first ionisation energy of Be is thus higher than that of Li.

In general, the first ionisation energy increases across a period because the nuclear
charge increases but the shielding remains the same.

Compare the first ionisation energies of Be (1s 22s2) and B (1s22s22p1).B has one
more proton in the nucleus than Be but there are also 2 extra inner sub-shell
electrons. These cancel out the charge of two more of the protons, leaving an
effective nuclear charge of only +1. This is less than Be (+2) so the electrons are
less strongly attracted to the nucleus and thus less difficult to remove.

The first ionisation energy of B is thus lower than that of Be.

Ionisation energies decrease from group II to group III because in group III the
electrons are removed from a p-orbital, so it is shielded by the s-electrons in the
outer shell. Thus the effective nuclear charge decreases.

From B (1s22s22p1) to N (1s22s22p3) the proton number increases, but the number of
electrons shielding the nuclear charge remains the same at 4. Thus the effective
nuclear charge increases from B to N and the electrons become progressively
harder to remove.

The first ionisation energy thus increases from B to N.

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So far the concepts of effective nuclear charge and shielding have been used to
explain the trend in first ionisation energies for the first 7 elements. They cannot,
however, explain the fall between N and O. The electronic configurations of N and
O must be considered more carefully:
1s 2s 2p
N ↑↓ ↑↓ ↑ ↑ ↑

O ↑↓ ↑↓ ↑↓ ↑ ↑

Note that in N the electron is removed from an unpaired orbital, but in O it is

removed from a paired orbital. In a paired orbital, the two electrons share a
confined space and so repel each other. They are therefore less stable and easier
to remove. This repulsion effect outweighs the higher effective nuclear charge in O.

The first ionisation energy of O is thus lower than that of N.

First ionisation energies decrease from group V to group VI, since the electron
removed from the group VI atom is paired, so there is more repulsion between the
electrons and the electron is easier to remove.

The first ionisation energies increase as expected from O to Ne, due to the increase
in effective nuclear charge.

The trend in first ionisation energies across period 2 can thus be summarised as
follows:

1. There is a general increase across the period as the nuclear charge increases
and the shielding remains the same.

2. There is a drop from Be to B because in B a 2p electron is being removed and

the extra shielding from the 2s subshell actually causes a fall in the effective
nuclear charge.

3. There is also a drop from N to O because the electron in O is being removed

from a paired orbital. The repulsion of the electrons in this orbital makes them
less stable and easier to remove.

The same trend can also be found in Period 3 (Na - Ar). There is a general
increase, but a drop between Mg and Al and also between P and S.

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Trend down a group

The above graph also shows a clear decrease in first ionisation energy on
descending a group. This can be explained in the following way:

On descending a group, the effective nuclear charge stays the same but the
number of inner shells increases. The repulsion between these inner shells and the
outer electrons makes them less stable, pushes them further from the nucleus and
makes them easier to remove.

ii) Successive ionisation energies

The second ionisation energy of an atom is the energy required to remove

one electron from each of a mole of free gaseous unipositive ions.

M +(g)  M2+(g) + e

Other ionisation energies can be defined in the same way:

The third ionisation energy of an atom is the energy required to remove one
electron from each of a mole of bipositive ions.

M 2+(g)  M3+(g) + e

The nth ionisation energy can be defined as the energy required for the process

M (n-1)+(g)  Mn+(g) + e

It always becomes progressively more difficult to remove successive electrons from

an atom; the second ionisation energy is always greater than the first, the third
always greater than the second and so on. There are two satisfactory explanations
for this:

As more electrons are removed from an atom, the number of electrons remaining in
the atom decreases. The repulsion between these electrons therefore decreases,
while the number of protons remains the same. The remaining electrons are thus
more stable and increasingly difficult to remove.

The difference in successive ionisation energies, however, varies widely and

depends on the electronic configuration of the atom in question. The difference in
successive ionisation energies of an atom can be predicted qualitatively by
consideration of the effective nuclear charge on the electron to be removed and the
shielding of that electron by the inner shell and inner sub-shell electrons.

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Consider the successive ionisation energies of aluminium, 1s22s22p63s23p1:

The 1st ionisation energy is fairly low because the 3p electron is shielded by all the
other electrons, and the effective nuclear charge is only +1.

The 2nd and 3rd ionisation energies are significantly higher than the 1 st because 3s
electrons are being removed and the effective nuclear charge on these electrons is +3.

1st: 578 kJmol-1, 2nd: 1817 kJmol-1, 3rd: 2745 kJmol-1

There is a huge jump to the 4th ionisation energy, since a 2p electron is now being
removed. The shielding has fallen and the effective nuclear charge has risen to +9.
The 5th and 6th ionisation energies are also high.

4th: 11578 kJmol-1, 5th: 14831 kJmol-1, 6th: 18378 kJmol-1

There is another significant jump to the 7 th ionisation energy, since an unpaired 2p

electron is now being removed.

7th: 23296 kJmol-1, 8th: 27460 kJmol-1, 9th: 31862 kJmol-1

The next significant jump is between the 9 th and 10th ionisation energies, since the
10th requires the removal of a 2s electron.

10th: 38458kJmol-1, 11th: 42655 kJmol-1

There is a huge jump to the12th ionisation energy, since a 1s electron is now being
removed.

12th: 201276kJmol-1, 13th: 222313kJmol-1.

These ionisation energies could be plotted on a graph as follows:

Variation of ionisation energy with number of

ionisations for aluminium

1000000
ionisation energy

100000

10000

1000

100
1 2 3 4 5 6 7 8 9 10 11 12 13
number of ionisations

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Note that the largest jumps by far occur between the 3rd and 4th ionisation energies,
and between the 11th and 12th ionisation energies. In practice only large jumps such
as this are visible on such a graph.
The relative values of successive ionisation energies are therefore a direct indicator
of the electronic configuration of the atom in question.

The trends can be summarised as follows:

1. The successive ionisation energies of an atom always increase. The more

electrons that are removed, the fewer the number electrons that remain. There
is therefore less repulsion between the electrons in the resulting ion. The
electrons are therefore more stable and harder to remove.

2. By far the largest jumps between successive ionisation energies come when the
electron is removed from an inner shell. This causes a large drop in shielding, a
large increase in effective nuclear charge and a large increase in ionisation
energy

By applying the above principles in reverse, it is also possible to predict the

electronic structure of a species by analysis of the successive ionisation energy
data:

Eg Si:

Variation of ionisation energy with number of

ionisations in silicon

1000000
ionisation energy

100000

10000

1000

100
1 3 5 7 9 11 13
number of ionisations

Large jumps occur between 4th and 5th and between 12th and 13th.

Therefore there are three shells: The first contains 2 electrons, the second 8 and
the third 4.

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Topic 1.2

AMOUNT OF SUBSTANCE
The mole
Reacting masses and atom economy
Solutions and titrations
The ideal gas equation
Empirical and molecular formulae
Ionic equations

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THE MOLE

Since atoms are so small, any sensible laboratory quantity of substance must
contain a huge number of atoms:
1 litre of water contains 3.3 x 1025 molecules.
1 gram of magnesium contains 2.5 x 1022 atoms.
100 cm3 of oxygen contains 2.5 x 1021molecules.

Such numbers are not convenient to work with, so it is necessary to find a unit of
"amount" which corresponds better to the sort of quantities of substance normally
being measured. The unit chosen for this purpose is the mole. The number is
chosen so that 1 mole of a substance corresponds to its relative
atomic/molecular/formula mass measured in grams. A mole is thus defined as
follows:

A mole of a substance is the amount of that substance that contains the

same number of elementary particles as there are carbon atoms in
12.00000 grams of carbon-12.

One mole of carbon-12 has a mass of 12.0g.

One mole of hydrogen atoms has a mass of 1.0g.
One mole of hydrogen molecules has a mass of 2.0g.
One mole of sodium chloride has a mass of 58.5g.

The number of particles in one mole of a substance is 6.02 x 10 23. This is known as
Avogadro's number, L.

Thus when we need to know the number of particles of a substance, we usually

count the number of moles. It is much easier than counting the number of particles.

The number of particles can be calculated by multiplying the number of moles by

Avogadro’s number. The number of moles can be calculated by dividing the number
of particles by Avogadro’s number.

(Number of particles) = (number of moles) x L

The mass of one mole of a substance is known as its molar mass, and has units of
gmol-1. It must be distinguished from relative atomic/molecular/formula mass, which
is a ratio and hence has no units, although both have the same numerical value.

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The symbol for molar mass of compounds or molecular elements is m r. The symbol
for molar mass of atoms is ar.

Mass (m), molar mass (mr or ar) and number of moles (n) are thus related by the
following equation:

MASS = MOLAR MASS X NUMBER OF MOLES

or m = mr x n

Mass must be measured in grams and molar mass in gmol-1.

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REACTING MASSES

It is possible to use the relationship moles = mass/m r to deduce the masses of

reactants and products that will react with each other.

When performing calculations involving reacting masses, there are two main points
which must be taken into account:

The total combined mass of the reactants must be the same as the total
combined mass of the products. This is known as the law of conservation of
mass.

The ratio in which species react corresponds to the number of moles, and not
their mass. Masses must therefore all be converted into moles, then compared to
each other, then converted back.

i) Reactions which go to completion

Eg. What mass of aluminium will be needed to react with 10 g of CuO, and what
mass of Al2O3 will be produced?

3CuO(s) + 2Al(s)  Al2O3(s) + 3Cu(s)

10 g
= 10/79.5
= 0.126 moles of CuO
3:2 ratio with Al
so 2/3 x 0.126 = 0.0839 moles of Al, so mass of Al = 0.0839 x 27 = 2.3 g
3:1 ratio with Al2O3
so 1/3 x 0.126 = 0.0419 moles of Al2O3, so mass of Al2O3 = 0.0419 x 102 = 4.3 g

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ii) Reactions which do not go to completion

Many inorganic reactions go to completion. Reactions which go to completion are

said to be quantitative. It is because the reactions go to completion that the
substances can be analysed in this way.

Some reactions, however, particularly organic reactions, do not go to completion. It

is possible to calculate the percentage yield of product by using the following
equation:

% yield = amount of product formed x 100

maximum amount of product possible

Eg 2.0 g of ethanol (C2H5OH) is oxidised to ethanoic acid (CH 3COOH). 1.9 g of

ethanoic acid is produced. What is the percentage yield? (assume 1:1 ratio)

Moles of ethanol = 2/46 = 0.0435

Max moles of ethanoic acid = 0.0435
so max mass of ethanoic acid = 0.0435 x 60 = 2.61 g
percentage yield = 1.9/2.61 x 100 = 73%

Eg When propanone (CH3COCH3) is reduced to propan-2-ol (CH3CH2CH2OH), a

76% yield is obtained. How much propan-2-ol can be obtained from1.4 g of
propanone? (assume 1:1 ratio)

Moles of propanone = 1.4/58 = 0.0241 moles

So max moles of propan-2-ol produced = 0.0241 moles
So actual amount produced = 0.0241 x 76/100 = 0.0183 moles
So mass of propan-2-ol = 0.0183 x 60 = 1.1 g

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ATOM ECONOMY

When we carry out a chemical reaction in order to make a product, we often make
other products, called by-products, as well.

Eg In the production of NaOH from NaCl the following reaction takes place:

2NaCl + 2H2O  2NaOH + H2 + Cl2

The atom economy of a reaction is the percentage of the total mass of reactants
that can, in theory, be converted into the desired product. It can be calculated as
follows:

% atom economy = mass of desired product x 100

total mass of products

Assuming we start with 2 moles of NaCl and 2 moles of H 2O, we will make 2 moles
of NaOH, and 1 mole of H2 and Cl2.

So % atom economy = (2 x 40) x 100 = 52.3 %

(2 x 40) + (1 x 2) + (1 x 71)

The remaining 47.7% of the mass is converted into less useful products and is
hence wasted.

So the higher the atom economy, the less waste and the more efficient the product
process (assuming the reaction does actually go to completion).

All reactions which have only one product have an atom economy of 100%

Atom economy is an important consideration when considering how to make a

particular useful product.

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SOLUTIONS

A solution is a homogeneous mixture of two or more substances in which the

proportions of the substances are identical throughout the mixture.

The major component of a solution is called the solvent and the minor components
are called the solutes. In most cases water is the solvent.

The amount of solute present in a fixed quantity of solvent or solution is called the
concentration of the solution. It is usually measured in grams of solute per dm 3 of
solution or in moles of solute per dm 3 of solution. In the latter case (moldm -3) it is
also known as the molarity of the solution.

The number of moles of solute, molarity of the solution and volume of solution can
thus be related by the equation:

Number of moles = volume x molarity

n=CxV

The volume of solution in this case must always be measured in dm 3 (or litres). If
the volumes are given in cm3 then V/1000 must be used instead.

If concentration is given in gdm-3, it must be converted to molarity before it can be

used in the above equation. This can be done easily by dividing by the molar mass
of the solute.

Concentration (gdm-3) = Molarity x molar mass

Or Cg = Cm x mr

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The volume of one solution required to react with a known volume of another can
be deduced from the above relationships and knowledge of the relevant chemical
equation. Remember it is moles which react in the ratio shown, so all quantities
must be converted to moles before the comparison can be made.

The quantitative investigation of chemical reactions by comparing reacting volumes

is known as volumetric analysis. The procedure by which reacting volumes are
determined is known as a titration.

In titrations, a solution whose concentration is unknown is titrated against a solution

whose concentration is known. The solution of known concentration is always
placed in the burette, and the solution of unknown concentration is always placed in
the conical flask.

Eg 28.3 cm3 of a 0.10 moldm-3 solution of NaOH was required to react with 25 cm 3
of a solution of H2SO4. What was the concentration of the H2SO4 solution?
Equation: H2SO4 + 2NaOH  Na2SO4 + 2H2O

Moles of NaOH = 28.3/1000 x 0.1 = 2.8 x 10-3

2:1 ratio so moles of H2SO4 = 2.8 x 10-3/2 = 1.4 x 10-3
so concentration of H2SO4 = 1.4 x 10-3/25 x 1000 = 0.056 moldm-3.

Eg Calculate the volume of 0.50 moldm -3 nitric acid required to react completely
with 5 g of lead (II) carbonate.
Equation: PbCO3 + 2HNO3  Pb(NO3)2 + CO2 + H2O

Moles of PbCO3 = 5/267 = 0.0187

1:2 ratio so moles of HNO3 = 0.0187 x 2 = 0.0375
Volume of HNO3 = 0.0375/0.5 x 1000 = 74.9 cm3.

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GASES

The volume occupied by a gas depends on a number of factors:

i) the temperature: the hotter the gas, the faster the particles are moving
and the more space they will occupy
ii) the pressure: the higher the pressure, the more compressed the gas will
be and the less space it will occupy
iii) the amount of gas: the more gas particles there are, the more space
they will occupy

The volume occupied by a gas does not depend on what gas it is, however: one
mole of any gas, at the same temperature and pressure, will have the same volume
as one mole of any other gas.

The pressure, temperature, volume and amount of gas can be related by a simple
equation known as the ideal gas equation:

PV = nRT

P is the pressure measured in pascals (Pa) or Nm -2. One atmosphere, which is

normal atmospheric pressure, is 101325 Pa.

V is the volume in m3. Remember; 1 m3 = 1000 dm3 = 106 cm3.

T is the absolute temperature, measured in Kelvin (K). Remember; 0 oC = 273 K.

R is the molar gas constant and has a value of 8.31 Jmol-1K-1.

This equation can be rearranged to find the density of gases and the RMM of
gases, using the relationship m = n x mr.

PV = mRT/mr, so the mass of one mole is given by m r = mRT/PV, where m is the

mass in kg. The answer m will also be in kg so it must be converted into grams.

The density of a gas, or mass/volume, is given by (m/V) = mrP/RT.

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SUMMARY – USING MOLES

Using the four relationships described, it is possible to calculate the amount of any
substance in a chemical reaction provided that the chemical equation is known and
the amount of one of the reacting species is also known. The procedure is
summarised in the table below:

These relationships are frequently used in practical chemistry. Typical calculations

in AS Practical Chemistry involve:

i) Determining the concentration of a solution

ii) Determining the relative molecular mass of a solid

iii) Determining the percentage purity of a solid

The percentage purity of a substance can be calculated as follows:

Percentage purity = mass substance would have if it was pure x 100

mass of impure substance

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EMPIRICAL AND MOLECULAR FORMULAE

The empirical formula of a compound is the formula which shows the simplest
whole-number ratio in which the atoms in that compound exist.
It can be calculated if the composition by mass of the compound is known.

The molecular formula of a substance is the formula which shows the number of
each type of atom in the one molecule of that substance.
It applies only to molecular substances, and can be deduced if the empirical
formula and molar mass of the compound are known.

The molecular formula is always a simple whole number multiple of the empirical
formula.

Eg a substance contains 85.8% carbon and 14.2% hydrogen, what is its empirical
formula? If its relative molecular mass is 56, what is its molecular formula?

Mole ratio = 85.8 : 14.2

12 1

= 7.15 : 14.2
7.15 : 7.15

= 1 : 2 so empirical formula = CH2

RMM = 56 = (CH2) so 14n = 56 and n = 56/14 = 4

Molecular formula = C4H8

It is also possible to calculate the percentage composition by mass of a substance,

if its empirical or molecular formula is known.

Eg What is the percentage composition by mass of ethanoic acid, C2H4O2?

RMM = 60

% C = (12 x 2)/60 x 100 = 40.0%

% H = (1 x 4)/60 x 100 = 6.67%

%O = (16 x 2)/60 x 100 = 53.3%

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FORMULAE OF IONIC COMPOUNDS

An ion is a species in which the number of electrons is not equal to the number of
protons. An ion thus has an overall charge, characteristic of the difference in the
number of protons and electrons. Ions with a positive charge are known as cations
and ions with a negative charge are known as anions.

Compounds made up of ions are known as salts. They are all electrically neutral,
so must all contain at least one anion and at least one cation.

Salts do not have molecular formulae, as they do not form molecules. They are
written as unit formulae.

The unit formula of an ionic compound is the formula which shows the simplest
whole number ratio in which the ions in the compound exist. This depends on the
charges of the ions involved. Some important ions and their charges are shown
below:

i) cations

Charge Formula Name

+1 Na+ Sodium
+1 K+ Potassium
+1 Ag+ Silver
+1 H+ Hydrogen
+1 NH4+ Ammonium
+1 Cu+ Copper(I)
+2 Mg2+ Magnesium
+2 Ca2+ Calcium
+2 Fe2+ Iron(II)
+2 Zn2+ Zinc
+2 Pb2+ Lead(II)
+2 Cu2+ Copper(II)
+2 Ni2+ Nickel(II)
+3 Al3+ Aluminium
+3 Cr3+ Chromium(III)
+3 Fe3+ Iron(III)

Note that some atoms can form more than one stable cation. In such cases it is
necessary to specify the charge that is on the cation by writing the charge in
brackets after the name of the metal.

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ii) anions

Charge Formula Name

-1 OH- Hydroxide
-2 SO42- Sulphate
-2 CO32- Carbonate
-1 NO3- Nitrate
-1 HCO3- Hydrogencarbonate

CHEMICAL EQUATIONS

The purpose of chemistry is essentially to study chemical reactions. In chemical

reactions, elements or compounds react with each other to form other elements
and/or other compounds.

Chemical reactions involve the movement of electrons between different species.

The nuclei always remain intact.

Every chemical reaction can be represented by a chemical equation. A chemical

equation indicates the species involved in the reaction and shows the way in which
they react. Every chemical equation must contain three pieces of information:

i) the identities of all the reactants and products

The chemical formulae of all the species involved in the reaction should be shown.
Any species left unchanged should be left out. Reactants must be written on the left
of the arrow and products on the right.

Remember that in chemical reactions all the nuclei remain unchanged. Therefore
the total number of atoms of each type must be the same on each side of the
equation. Atoms themselves cannot be created or destroyed in chemical reactions;
only transferred from species to species.

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ii) the reaction coefficients

Atoms, elements and compounds combine with each other in simple whole number
ratios, eg 1:1, 1:2, 1:3. The ratio in which the species react and in which products
are formed are shown in the reaction coefficients. These are the numbers which
precede the chemical formula of each species in the equation. If no coefficient is
shown it is assumed to be 1.

Deducing the reaction coefficients for a reaction is known as balancing the

equation. The total number of atoms of each element must be the same on both
sides of the equation.

When balancing chemical equations, always balance compounds first and elements
second. It's easier that way.

N.B. Reaction coefficients in no way show the actual amount of a substance which
is reacting. They provide information only on the way in which they react.

iii) The state symbols

The state symbol shows the physical state of each reacting species and must be
included in every chemical equation. There are four state symbols required for A-
level chemistry:
(s) - solid
(l) - liquid
(g) - gas
(aq) - aqueous, or dissolved in water

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IONIC EQUATIONS

Many reactions that take place in aqueous solution do not involve all of the ions that
are written in the equation. Some species remain in aqueous solution before and
after the reaction. They therefore play no part in the reaction and are known as
spectator ions.

In ionic equations, spectator ions are left out.

Eg BaCl2(aq) + Na2SO4(aq)  BaSO4(s) + 2NaCl(aq)

This reaction involves the precipitation of barium sulphate.
Notice that the Cl- ions and the Na+ ions remain in the aqueous state before and
after the reaction. They are therefore spectator ions.
The above reaction can then be rewritten as follows:
Ba2+(aq) + SO42-(aq)  BaSO4(s)

Eg Al2(SO4)3(aq) + 6NaOH(aq)  2Al(OH)3(s) + 3Na2SO4(aq)

This reaction involves the precipitation of aluminium hydroxide.
The Na+ and SO42- ions are spectator ions and can be left out
The ionic equation for the reaction is:
Al3+(aq) + 3OH-(aq)  Al(OH)3(s)

Ionic equations are very useful for simplifying precipitation reactions.

They can also simplify acid-base reactions:

Eg NaOH(aq) + HCl(aq)  NaCl(aq) + H2O(l)

The Na+ and Cl- ions are spectator ions, so the ionic equation for the reaction is:

H+(aq) + OH-(aq)  H2O(l)

All reactions between strong acids and strong alkalis have the same ionic equation.

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Topic 1.3

BONDING
Types of bond
States of matter
Structure and physical properties
Molecular shapes
Intermolecular forces

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TYPES OF BOND

Atoms bond to each other in one of four ways:

Ionic Bonding

An ionic bond is an attraction between oppositely charged ions, which are

formed by the transfer of electrons from one atom to another.

Eg In sodium chloride, each sodium atom transfers an electron to a chlorine atom.

The result is a sodium ion and a chloride anion. These two ions attract each other
to form a stable compound.

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Covalent Bonding

A covalent bond is a pair of electrons shared between two atoms.

In a normal covalent bond, each atom provides one of the electrons in the bond. A
covalent bond is represented by a short straight line between the two atoms.

Eg water

In a dative covalent bond, one atom provides both electrons to the bond.

A dative covalent bond is a pair of electrons shared between two atoms, one
of which provides both electrons to the bond.

A dative covalent bond is represented by a short arrow from the electron providing
both electrons to the electron providing neither.

Eg ammonium ion

Covalent bonding happens because the electrons are more stable when attracted
to two nuclei than when attracted to only one.

Covalent bonds should not be regarded as shared electron pairs in a fixed position;
the electrons are in a state of constant motion and are best regarded more as
charge clouds.

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Metallic Bonding

A metallic bond is an attraction between cations and a sea of electrons.

Metallic bonds are formed when atoms lose electrons and the resulting electrons
are attracted to all the resulting cations.

Eg Magnesium atoms lose two electrons each, and the resulting electrons are
attracted to all the cations.

Metallic bonding happens because the electrons are attracted to more than one
nucleus and hence more stable. The electrons are said to be delocalized – they are
not attached to any particular atom but are free to move between the atoms.

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IONIC OR COVALENT? - ELECTRONEGATIVITY

Electronegativity is the relative ability of an atom to attract electrons in a

covalent bond.

The electronegativity of an atom depends on its ability to attract electrons and its
ability to hold onto electrons. Electronegativity increases across a period as the
nuclear charge on the atoms increases but the shielding stays the same, so the
electrons are more strongly attracted to the atom. Electronegativity decreases down
a group as the number of shells increases, so shielding increases and the electrons
are less strongly attracted to the atom.

An atom which has a high electronegativity is said to be electronegative; an atom

which does not have a high electronegativity is said to be electropositive.

Electronegativities are relative; electronegativity has no units and is measured on a

scale from 0.7 to 4.0. The electronegativities of some elements in the periodic table
are shown below:

H He
2.1
Li Be B C N O F Ne
1.0 1.5 2.0 2.5 3.0 3.5 4.0
Na Mg Al Si P S Cl Ar
0.9 1.2 1.5 1.8 2.1 2.5 3.0
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
0.8 1.0 1.3 1.5 1.6 1.6 1.5 1.8 1.8 1.8 1.9 1.6 1.6 1.8 2.0 2.4 2.8

Note that the noble gases cannot be ascribed an electronegativity since they do not
form bonds.

Electronegativity is a very useful concept for predicting whether the bonding

between two atoms will be ionic, covalent or metallic.

Consider a covalent bond between two atoms A and B.

If both atoms have a similar electronegativity, both atoms attract the electrons with
similar power and the electrons will remain midway between the two. The bond will
thus be covalent - the electrons are shared between the two atoms.

Eg H (2.1) and H (2.1)

a covalent bond

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If one atom is significantly more electronegative than the other, it attracts the
electrons more strongly than the other and the electrons are on average closer to
one atom than the other. The electrons are still shared, but one atom has a slight
deficit of electrons and thus a slight positive charge and the other a slight surplus of
electrons and thus a slight negative charge. Such a bond is said to be polar
covalent.

Eg H (2.1) and O (3.0)

a polar covalent bond

A slight positive charge or negative charge on an atom is represented by a  or a

 symbol respectively.

If the difference between the two atoms is large, then the sharing of electrons is so
uneven that the more electronegative atom has virtually sole possession of the
electrons. The electrons are, in effect, not shared at all but an electron has
essentially between transferred from one atom to the other. The more
electropositive atom is positively charged and the more electronegative atom is
negatively charged. The bonding is thus ionic.

Eg Na (0.9) and Cl (3.0)

an ionic bond

If both atoms are electropositive, neither has a great ability to attract electrons and
the electrons do not remain localised in the bond at all. They are free to move, both
atoms gain a positive charge and the bonding is metallic.

Eg Mg (1.2) and Mg (1.2)

a metallic bond

Differences in electronegativity can be used to predict how much ionic or metallic

character a covalent bond will have.

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Given suitable electronegativity data, it is thus possible to predict whether a bond

between two atoms will be ionic, polar covalent, covalent or metallic.

If both atoms have electronegativities less than 1.6 - 1.9 then the bond is metallic.

If either atom has an electronegativity greater than 1.9 and the difference is less
than 0.5 then the bond is covalent.

If either atom has an electronegativity greater than 1.9 and the difference is more
than 0.5 but less than 2.1 then the bond is polar covalent.

If the difference is greater than 2.1 then the bond is ionic.

These rules are not perfect and there are notable exceptions; for example the bond
between Si (1.8) and Si (1.8) is covalent but the bond between Cu (1.9) and Cu
(1.9) is metallic. The bond between Na (0.9) and H (2.1) is ionic but the bond
between Si (1.8) and F (4.0) is polar covalent. However as basic giudelines they are
very useful provided that their limitations are appreciated.

All bonds are assumed to be covalent in principle: differences in electronegativity can be

used to predict how much ionic or metallic character a covalent bond will have.

Electronegativity differences show that bonds between non-identical atoms are all
essentially intermediate in character between ionic and covalent. No bond is completely
ionic, and only bonds between identical atoms are completely covalent.

Bonds between identical atoms cannot be ionic as there is no difference in

electronegativity. They will therefore be either covalent or metallic.

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STATES OF MATTER

Matter can exist in one of three states; solid, liquid and gas. The state in which a
certain substance is most stable at a given temperature depends on the balance
between the kinetic energy of the particles, which depends on temperature, and the
magnitude of the force of attraction between them.

Solids

In a solid, the particles are tightly packed together in a lattice. A lattice is an ordered
and infinitely repeating arrangement of particles. The properties of solids are
dominated by the forces in between these particles which cause them to attract
each other and preserve this ordered arrangement.

A solid thus has a fixed volume and a fixed shape.

At all temperatures above absolute zero, the particles have kinetic energy. In a
solid, however, this kinetic energy is not enough to cause the particles to fly apart,
and nor is it enough to cause significant separation of the particles. The particles
are thus restricted to rotational and vibrational motion; no translational motion of the
particles with respect to each other is possible.

In a solid, the kinetic energy of the particles is not nearly enough to overcome the
potential energy caused by their mutual attraction.

SOLIDS

If a solid is heated, the kinetic energy of the particles increases, and they vibrate
more. As they vibrate more, the bonds between the particles are weakened, some
are broken and spaces appear between the particles. At this point the solid has
melted.

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Liquids

In a liquid, the particles are by and large packed together in a lattice that extends
across the range of 10 - 100 particles. However over a longer range the structure
breaks down, and there is enough space between the particles for them to move
from one cluster to another. The properties of liquids are still dominated by the
forces between the particles, but these particles have enough kinetic energy to
move between each other in the spaces that exist. There is thus short-range order
but no long-range order.

A liquid has a fixed volume but no fixed shape.

The kinetic energy of the particles is now significant; it forces the particles apart to
the extent that the spaces between them are often wider than the particles
themselves. The particles are thus permitted some translational motion with respect
to each other within these spaces. All solids will melt if they are heated strongly
enough.

In a liquid, the kinetic energy of the particles is still not large enough to overcome
their mutual attraction, but is nevertheless significant and must be taken into
account.

LIQUIDS

Gases
In a gas, all the particles are in rapid and random motion, and thus behave
independently of each other. There is no ordered arrangement of any kind, and the
spaces between the particles are much larger than the size of the particles
themselves. The properties of a gas are dominated by the kinetic energy of the
particles; the attraction between them is not significant.

A gas has neither a fixed volume nor a fixed shape.

In a gas, the kinetic energy of the particles is much greater than the forces of
attraction between them. Since the kinetic energy depends only on temperature, it
follows that all gases at a similar temperature behave in a similar way. All liquids
can be boiled if heated strongly enough.

GASES

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IONIC STRUCTURES

Bonding in ionic compounds

An ionic bond is an attraction between oppositely charged ions. After the ions are
formed they all come together to form a lattice. A lattice is an infinite and repeating
arrangement of particles. All the anions are surrounded by cations and all the
cations are surrounded by anions.

The coordination number of an ion in an ionic solid is the number of oppositely

charged ions which surround it. This varies from substance to substance but is
usually 4, 6 or 8.

Example – sodium chloride

In sodium chloride, NaCl, each sodium ion is surrounded by six chloride ions and
vice versa.

The diagram below shows the structure of sodium chloride. The pattern repeats in
this way and the structure extends (repeats itself) in all directions over countless
ions. You must remember that this diagram represents only a tiny part of the whole
sodium chloride crystal.

Each sodium ion attracts several

chloride ions and vice versa so the
ionic bonding is not just between one
sodium and one chloride ion. There is
a 3-D lattice.

It could also be represented as follows:

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1. Melting and boiling point

The attraction between opposite ions is very strong. A lot of kinetic energy is thus
required to overcome them and the melting point and boiling point of ionic
compounds is very high.

In the liquid state, the ions still retain their charge and the attraction between the
ions is still strong. Much more energy is required to separate the ions completely
and the difference between the melting and boiling point is thus large.

Compound NaCl MgO

Melting point/oC 801 2852
Boiling point/oC 1459 3600

The higher the charge on the ions, and the smaller they are, the stronger the
attraction between them will be and the higher the melting and boiling points. In
MgO, the ions have a 2+ and 2- charge and thus the attraction between them is
stronger than in NaCl, so the melting and boiling points are higher.

2. Electrical Conductivity

Since ionic solids contain ions, they are attracted by electric fields and will, if possible,
move towards the electrodes and thus conduct electricity. In the solid state, however,
the ions are not free to move since they are tightly held in place by each other. Thus
ionic compounds do not conduct electricity in the solid state. Ionic solids are thus good
insulators.

In the liquid state, the ions are free to move and so can move towards their respective
electrodes. Thus ionic compounds can conduct electricity in the liquid state.

3. Mechanical properties

Since ions are held strongly in place by the other ions, they cannot move or slip over
each other easily and are hence hard and brittle.

opposite ions attract like ions repel – structure breaks

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METALLIC STRUCTURES

Bonding in metals

Metallic bonding is the attraction between cations and a sea of delocalised

electrons. The cations are arranged to form a lattice, with the electrons free to move
between them.

The structure of the lattice varies from metal to metal, and they do not need to be
known in detail. It is possible to draw a simplified form of the lattice:

Example - magnesium

This is a
simplified 2D
form of the
metal lattice

Properties of metals

a) Electrical conductivity: since the electrons in a metal are delocalised, they are
free to move throughout the crystal in a certain direction when a potential difference
is applied and metals can thus conduct electricity in the solid state. The delocalised
electron system is still present in the liquid state, so metals can also conduct
electricity well in the liquid state.

b) Melting and boiling point: although not generally as strong as in ionic

compounds, the bonding in metals is relatively strong, and as a result the melting
and boiling points of metals are relatively high.

Metal Na K Be Mg
Melting point/ oC 98 64 127 649
8
Boiling point/ oC 883 760 297 110
0 7

Smaller ions, and those with a high charge, attract the electrons more strongly and
so have higher melting points than larger ions with a low charge. Na has smaller
cations than K so has a higher melting and boiling point. Mg cations have a higher
charge than Na so has a higher melting and boiling point.

c) Other physical properties: Since the bonding in metals is non-directional, it

does not really matter how the cations are oriented relative to each other. The metal
cations can be moved around and there will still be delocalized electrons available

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to hold the cations together. The metal cations can thus slip over each other fairly
easily. As a result, metals tend to be soft, malleable and ductile.

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COVALENT STRUCTURES

A covalent bond is a shared pair of electrons between two atoms. When a covalent
bond is formed, two atomic orbitals overlap and a molecular orbital is formed. Like
atomic orbitals, a molecular orbital can only contain two electrons. Overlap of
atomic orbitals is thus only possible if both orbitals contain only one electron
(normal covalent bond), or if one is full and the other empty (dative covalent bond).

Covalent bonding happens because the electrons are more stable when attracted
to two nuclei than when attracted to only one:

Normal covalent bonds

An overlap between two orbitals, each containing one electron, is a normal covalent
bond. The number of normal covalent bonds which an atom can form depends on
its number of unpaired electrons. Some atoms, like carbon, promote electrons from
s to p orbitals to create unpaired electrons.

1s 2s 2p
F ↑↓ ↑↓ ↑↓ ↑↓ ↑
F has 1 unpaired electron in a 2p orbital – forms one covalent bond

Eg hydrogen fluoride

1s 2s 2p
C ↑↓ ↑↓ ↑ ↑

Carbon rearranges slightly to make more unpaired electrons –

1s 2s 2p
C ↑↓ ↑ ↑ ↑ ↑
C has 4 unpaired electrons – forms four covalent bonds

Eg methane

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Dative covalent bonds

Any atom which has filled valence shell orbitals can provide both electrons for a
dative covalent bond. This includes any element in groups V, VI, VII or 0 but is most
common in N, O and Cl.

1s 2s 2p
N ↑↓ ↑↓ ↑ ↑ ↑
N has three unpaired electrons and one electron pair

Any atom which has empty valence shell orbitals can accept a pair of electrons for
a covalent bond. This includes any element in groups I, II and III but is most
common in Be, B and Al.

1s 2s 2p
B ↑↓ ↑↓ ↑

B promotes an electron from 2s to 2p to form 3 unpaired electrons:

1s 2s 2p
B ↑↓ ↑ ↑ ↑
B has 3 unpaired electrons and an empty orbital

Eg BH3NH3

Sigma and pi bonds

Atomic orbitals can overlap in one of two ways:

If they overlap directly along the internuclear axis, as is most common, a -bond is
formed.

A -bond is a bond resulting from direct overlap of two orbitals along the
internuclear axis.
All single bonds between two atoms are -bonds.
It is only possible to form one -bond between two atoms, since another would force
too many electrons into a small space and generate repulsion. If double bonds are
formed, therefore, the orbitals must overlap in a different way.

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If two orbitals overlap above and below (or behind and in front of) the internuclear
axis, then a -bond is formed.

A -bond is a bond resulting from overlap of atomic orbitals above and below
the internuclear axis.
All double bonds consist of a -bond and a -bond.

All triple bonds consist of a -bond and two -bonds. If the first -bond results from
overlap above and below the internuclear axis, the second results from overlap
behind and in front of the internuclear axis.

Note that -bonds can only be formed by overlap of p-orbitals, since s-orbitals do
not have the correct geometry.

-bonds can also be represented by orbital diagrams.

Eg ethene:

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Strength of covalent bonds

Covalent bonds are in general strong. The smaller the atoms, the closer the
electrons are to the two nuclei and the stronger the bond.

Bond Bond dissociation energy/ kJmol-1

C-F 467
C-Cl 346
C-Br 290
C-I 228

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Molecular, giant covalent and layered substances

Covalent bonding can result in three very different types of substance:

Molecular

In many cases, the bonding capacity is reached after only a few atoms have
combined with each other to form a molecule. If no more covalent bonds can be
formed after this, the substance will be made up of a larger number of discreet units
(molecules) with no strong bonding between them.
Such substances are called molecular substances, and there are many examples
of them: CH4, Cl2, He, S8, P4, O2, H2O, NH3 etc

The molecules are held together by intermolecular forces, which are much
weaker than covalent bonds but are often strong enough to keep the substance in
the solid or liquid state.

Example - Iodine

There are attractive forces between these molecules, known as intermolecular

forces, but they are weak. In the gaseous state, the intermolecular forces are
broken but the bonds within the molecule remain intact - they are not broken. The
gas phase consists of molecules, not atoms.

Molecular substances have certain characteristic properties:

Melting and boiling point: these are generally low, since intermolecular forces are
weak.
Intermolecular forces also decrease rapidly with increasing distance, so there is
often little difference in the melting and boiling points.

Substance CH4 H2O H2 He

Melting point /oC -184 0 -259 -272
Boiling point /oC -166 100 -253 -268

Electrical conductivity: There are no ions and no delocalised electrons, so there is

little electrical conductivity in either solid or liquid state.

Other physical properties: The intermolecular forces are weak and generally non-
directional, so most molecular covalent substances are soft, crumbly and not very
strong.

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Giant covalent

In some cases, it is not possible to satisfy the bonding capacity of a substance in

the form of a molecule; the bonds between atoms continue indefinitely, and a large
lattice is formed. There are no discrete molecules and covalent bonding exists
between all adjacent atoms.
Such substances are called giant covalent substances, and the most important
examples are C, B, Si and SiO2.

Example – diamond (diamond is an allotrope of carbon)

Don't forget that this is just a tiny part

of a giant structure extending on all 3
dimensions.

In giant covalent compounds, covalent bonds must be broken before a substance

can melt or boil.

Giant covalent compounds have certain characteristic properties:

Melting and boiling point: these are generally very high, since strong covalent
bonds must be broken before any atoms can be separated. The melting and boiling
points depend on the number of bonds formed by each atom and the bond strength.
The difference between melting and boiling points is not usually very large, since
covalent bonds are very directional and once broken, are broken completely.

Substance C Si B SiO2
Melting point /oC 3550 1410 2300 1510
Boiling point /oC 4827 2355 2550 2230

Electrical conductivity: there are no ions or delocalised electrons, so there is little

electrical conductivity in either solid or liquid state.

Other physical properties: since the covalent bonds are strong and directional, giant
covalent substances are hard, strong and brittle.
Diamond is in fact the hardest substance known to man. For this reason it is used in
drills, glass-cutting and styluses for turntables.

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Giant covalent layered

Some substances contain an infinite lattice of covalently bonded atoms in two

dimensions only to form layers. The different layers are held together by
intermolecular forces, and there are often delocalized electrons in between the
layers. Examples of these structures are graphite and black phosphorus.

Example - graphite

or

In graphite, each carbon atom is bonded to three others. The spare electron is
delocalized and occupies the space in between the layers. All atoms in the same
layer are held together by strong covalent bonds, and the different layers are held
together by intermolecular forces.

A number of characteristic properties of graphite result from this structure:

Electrical conductivity: due to the delocalised electrons in each plane, graphite is a
very good conductor of electricity in the x and y directions, even in the solid state
(unusually for a non-metal). However, since the delocalisation is only in two
dimensions, there is little electrical conductivity in the z direction (i.e. perpendicular
to the planes).
Density: graphite has a much lower density than diamond (2.25 gcm -3) due to the
relatively large distances in between the planes.
Hardness: graphite is much softer than diamond since the different planes can slip
over each other fairly easily. This results in the widespread use of graphite in
pencils and as an industrial lubricant.

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SUMMARY OF DIFFERENT TYPES OF COMPOUND AND THEIR PROPERTIES

SUBSTANCE Nature of bonding Physical properties

IONIC Attraction between oppositely High mpt, bpt

charged ions. Good conductors in liquid state
Eg NaCl Infinite lattice of oppositely Poor conductors in solid state
charged ions in three dimensions Hard, strong, brittle

METALLIC Attraction between cations and High mpt, bpt

delocalised electrons. Good conductors in solid state
Eg Mg Infinite lattice of cations in three Good conductors in liquid state
dimensions, with delocalized Strong, malleable
electrons in the spaces

GIANT COVALENT Infinite lattice of atoms linked by Very high mpt, bpt
covalent bonds in three Poor conductors in solid state
Eg diamond dimensions. Poor conductors in liquid state
Covalent bonds are pairs of Hard, strong, brittle
electrons shared between two
atoms

MOLECULAR Discrete molecules. Atoms in Low mpt, bpt

molecule linked by covalent bonds. Poor conductors in solid state
Eg I2 ( or , normal or dative) Poor conductors in liquid state
Weak intermolecular forces Soft, weak, powdery
between molecules.

GIANT COVALENT Infinite lattice of atoms linked by High mpt, bpt

LAYERED covalent bonds in two dimensions Good conductors parallel to planes
to form planes. Poor conductors perpendicular to
Planes held together by planes
Eg graphite
intermolecular forces. Soft
Delocalised electrons in between
layers

Don’t forget to learn the structures of

 Sodium chloride

 Iodine

 Diamond

 Graphite

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MOLECULAR SHAPES

When an atom forms a covalent bond with another atom, the electrons in the
different bonds and the non-bonding electrons in the outer shell all behave as
negatively charged clouds and repel each other. In order to minimise this repulsion,
all the outer shell electrons spread out as far apart in space as possible.

Molecular shapes and the angles between bonds can be predicted by the VSEPR
theory
VSEPR = valence shell electron pair repulsion

VSEPR theory consists of two basic rules:

i) All -bonded electron pairs and all lone pairs arrange themselves as far apart
in space as is possible. -bonded electron pairs are excluded.
ii) Lone pairs repel more strongly than bonding pairs.

These two rules can be used to predict the shape of any covalent molecule or ion,
and the angles between the bonds.

a) 2 electron pairs
If there are two electron pairs on the central atom, the angle between the bonds is
180o.

Molecules which adopt this shape are said to be LINEAR.

E.g. BeCl2, CO2
b) three electron pairs
If there are three electron pairs on the central atom, the angle between the bonds is
120o.

Molecules which adopt this shape are said to be TRIGONAL PLANAR.

E.g. BF3, AlCl3, CO32-, NO3-

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If one of these electron pairs is a lone pair, the bond angle is slightly less than 120 o
due to the stronger repulsion from lone pairs, forcing them closer together.

bond angle = 118o

Molecules which adopt this shape are said to be BENT.

E.g. SO2, NO2-

c) Four electron pairs

If there are four bonded pairs on the central atom, the angle between the bonds is
approx 109o.

Molecules which adopt this shape are said to be TETRAHEDRAL.

E.g. CH4, SiCl4, NH4+, SO42-

If one of the electron pairs is a lone pair, the bond angle is slightly less than 109 o,
due to the extra lone pair repulsion which pushes the bonds closer together (approx
107o).

Molecules which adopt this shape are said to be TRIGONAL PYRAMIDAL.

E.g. NH3, PCl3

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If two of the electron pairs are lone pairs, the bond angle is also slightly less than
109o, due to the extra lone pair repulsion (approx 104o).

Molecules which adopt this shape are said to be BENT.

E.g. H2O, OF2

d) Five electron pairs

If there are five bonded pairs on the central atom, the three bonds are in a plane at
120o to each other, the other 2 are at 90 o to the plane.

Molecules which adopt this shape are said to be TRIGONAL BYPRYMIDAL.

E.g. PF5, PCl5

d) Six electron pairs

If there are six electron pairs on the central atom, the angle between the bonds is
90o.

Molecules which adopt this shape are said to be OCTAHEDRAL.

E.g. SF6

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If there are 4 bonding pairs and 2 lone pairs, the bonded pairs are at 90 o in the
plane and the lone pairs at 180o. The angles are still exactly 90o because the lone
pairs are opposite each other so their repulsion cancels out.

Molecules which adopt this shape are said to be SQUARE PLANAR.

E.g. XeF4, ClF4-

SUMMARY OF MOLECULAR SHAPES

Valence shell Bonding Lone shape Bond

electron pairs pairs pairs Angle (o)
2 2 0 LINEAR 180

3 3 0 TRIGONAL PLANAR 120

3 2 1 BENT 115 - 118

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4 4 0 TETRAHEDRAL 109.5

4 3 1 TRIGONAL 107
PYRAMIDAL

4 2 2 BENT 104.5

5 5 0 TRIGONAL 90 and 120

BIPYRAMIDAL

6 6 0 OCTAHEDRAL 90

6 4 2 SQUARE PLANAR 90

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INTERMOLECULAR FORCES

There are no covalent bonds between molecules in molecular covalent compounds.

There are, however, forces of attraction between these molecules, and it is these
which must be overcome when the substance is melted and boiled. These forces
are known as intermolecular forces. There are three main types of intermolecular
force:

1. Van der Waal's forces

Consider a molecule of oxygen, O2.

The electrons in this molecule are not static; they are in a state of constant motion.
It is therefore likely that at any given time the distribution of electrons will not be
exactly symmetrical - there is likely to be a slight surplus of electrons on one of the
atoms.

This is known as a temporary dipole. It lasts for a very short time as the electrons
are constantly moving. Temporary dipoles are constantly appearing and
disappearing.

Consider now an adjacent molecule. The electrons on this molecule are repelled by
the negative part of the dipole and attracted to the positive part, and move
accordingly.

This is known as an induced dipole. There is a resulting attraction between the

two molecules, and this known as a Van der Waal's force.

Van der Waal's forces are present between all molecules, although they can be
very weak. They are the reason all compounds can be liquefied and solidified. Van
der Waal's forces tend to have strengths between 1 kJmol-1 and 50 kJmol-1.

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The strength of the Van der Waal's forces in between molecules depends on two
factors:

a) the number of electrons in the molecule

The greater the number of electrons in a molecule, the greater the likelihood of a
distortion and thus the greater the frequency and magnitude of the temporary
dipoles. Thus the Van der Waal's forces between the molecules are stronger and
the melting and boiling points are larger.

Eg noble gases:

Substance He Ne Ar Kr
Number of electrons 2 10 18 36
Melting point/oC -272 -252 -189 -157
Boiling point/oC -269 -250 -186 -152

Eg alkanes:

Substance CH4 C2H6 C3H8 C4H10

Number of electrons 10 18 26 34
Melting point/oC -182 -183 -190 -138
Boiling point/oC -164 -88 -42 0

a) Surface area of the molecules

The larger the surface area of a molecule, the more contact it will have with
adjacent molecules. Thus the greater its ability to induce a dipole in an adjacent
molecule and the greater the Van der Waal's forces and melting and boiling points.

This point can be illustrated by comparing different molecules containing a similar

number of electrons:

Substance Kr Cl2 CH3CH(CH3)CH3 CH3CH2CH2CH3

Number of 36 34 34 34
electrons
Melting point/oC -157 -101 -159 -138
Boiling point/oC -152 -35 -12 0

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CH3CH(CH3)CH3 CH3CH2CH2CH3
methylpropane butane

Note that butane has a larger surface area than 2-methylpropane, although they
have the same molecular formula (C4H10). Straight-chain molecules always have
higher boiling points than their isomers with branched chains.

2. Dipole-dipole bonding

Temporary dipoles exist in all molecules, but in some molecules there is also a
permanent dipole.

Most covalent bonds have a degree of ionic character resulting from a difference in
electronegativity between the atoms. This results in a polar bond and a dipole.

In many cases, however, the presence of polar bonds (dipoles) does not result in a
permanent dipole on the molecule, as there are other polar bonds (dipoles) in the
same molecule which have the effect of cancelling each other out. This effect can
be seen in a number of linear, trigonal planar and tetrahedral substances:

CO2 BF3
CCl4

In all the above cases, there are dipoles resulting from polar bonds but the vector
sum of these dipoles is zero; i.e. the dipoles cancel each other out. The molecule
thus has no overall dipole and is said to be non-polar.

Non-polar molecules are those in which there are no polar bonds or in which the
dipoles resulting from the polar bonds all cancel each other out. The only
intermolecular forces that exist between non-polar molecules are temporary-
induced dipole attractions, or Van der Waal’s forces.

In other molecules, however, there are dipoles on the molecule which do not cancel
each other out:

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CHCl3 SO2 NH3

In all the above cases, there are dipoles resulting from polar bonds whose vector
sum is not zero; i.e. the dipoles do not cancel each other out. The molecule thus
has a permanent dipole and is said to be polar.

Polar molecules are those in which there are polar bonds and in which the dipoles
resulting from the polar bonds do not cancel out.

In addition to the Van der Waal's forces caused by temporary dipoles, molecules
with permanent dipoles are also attracted to each other by dipole-dipole bonding.
This is an attraction between a permanent dipole on one molecule and a permanent
dipole on another.

Dipole-dipole bonding usually results in the boiling points of the compounds being
slightly higher than expected from temporary dipoles alone; it slightly increases the
strength of the intermolecular bonding.
The effect of dipole-dipole bonding can be seen by comparing the melting and
boiling points of different substances which should have Van der Waal's forces of
similar strength:

Substance Cl2 HBr CH3CH(CH3)CH3 CH3COCH3

Number of 34 36 34 32
electrons
Permanent NO YES NO YES
dipole
Melting -101 -88 -159 -95
point/oC
Boiling -45 -67 -73 -44
point/oC

3. Hydrogen bonding

In most cases as seen above, the presence of permanent dipoles only makes a
slight difference to the magnitude of the intermolecular forces. There is one

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exceptional case, however, where the permanent dipole makes a huge difference to
the strength of the bonding between the molecules.

Consider a molecule of hydrogen fluoride, HF. This clearly has a permanent dipole
as there is a large difference in electronegativity between H (2.1) and F (4.0). The
electrons in this bond are on average much closer to the F than the H:

The result of this is that the H atom has on almost no electron density around its
nucleus at all and is therefore very small. The H atom is therefore able to approach
electronegative atoms on adjacent molecules very closely and form a very strong
intermolecular dipole-dipole bond.

This is known as hydrogen bonding. It is only possible if the hydrogen atom is

bonded to a very electronegative element; i.e. N, O or F. It is not fundamentally
different from dipole-dipole bonding; it is just a stronger form of it.

A hydrogen bond can be defined as an attraction between an electropositive

hydrogen atom (ie covalently bonded to N, O or F) and an electronegative atom on
an adjacent molecule.

Examples of substances containing hydrogen bonds are HF, H2O, NH3, alcohols,
carboxylic acids, amines, acid amides and urea.

a) Effect on boiling point

The effect of hydrogen bonding on melting and boiling points of substances is huge,
unlike other dipole-dipole bonds. Many substances containing hydrogen bonds
have much higher boiling points than would be predicted from Van der Waal's
forces alone.

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Substance CH3OCH3 CH3CH2OH CH3CH2CH2CHO CH3CH2COOH

Structure H H H O H H
O
CH3 CH2 OH
H C C C C H H C C C

H H H OH
H H

Number of 26 26 40 40
electrons
Hydrogen NO YES NO YES
bonding
Melting -95 -117 -81 -21
point/oC
Boiling -44 79 56 141
point/oC

Another important series of trends are the boiling points of the hydrides of elements
in groups V, VI and VII of the periodic table:
Group V: NH3, PH3, AsH3, SbH3
Group VI: H2O, H2S, H2Se, H2Te
Group VII: HF, HCl, HBr, HI

The boiling points of these graphs are shown graphically below:

Graph to show how hydrogen bonding affects boiling point

150
boiling point (degrees celcius)

100 H2O

50

HF
0 H2Te
0 20 40 60 80 100 120 SbH3
140
NH3
H2Se HI
-50 AsH3
H2S HBr
HCl
PH3
-100
relative m oleular m ass

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In each case the hydride of period 2 shows a boiling point which is abnormally high
( H2O, NH3 and HF).

The general increase in boiling point down the groups result from the increase in
Van der Waal's forces which results from an increasing number of electrons in the
molecules. There are permanent dipoles but they are not very strong.

The abnormally high boiling points of H 2O, NH3 and HF are a result of hydrogen
bonding between the molecules. Thus results in very strong intermolecular forces
between the molecules despite the fact that the Van der Waal's forces are weaker
than in the other hydrides.

b) other effects of hydrogen bonding

The effects of hydrogen bonding on the physical properties of a substance are not
restricted to elevated melting and boiling points; it can influence the properties of
substances in other ways:

The low density of ice. This is due to hydrogen bonding. In ice, the water
molecules arrange themselves in such a way as to maximise the amount of
hydrogen bonding between the molecules. This results in a very open hexagonal
structure with large spaces within the crystal. This accounts for its low density.

When the ice melts, the structure collapses into the open spaces and the resulting
liquid, despite being less ordered, occupies less space and is thus more dense.

Thus ice floats on water.

The helical nature of DNA. This is also due to hydrogen bonding. Molecules of
DNA contain N-H bonds and so hydrogen bonding is possible. The long chains also
contain C=O bonds and the H atoms can form a hydrogen bond with this
electronegative O atom. This results in the molecule spiralling, as the C=O bonds
and the N-H bonds approach each other.

This is an example of an intramolecular hydrogen bond, where the attraction is

between a hydrogen atom and an electronegative atom on the same molecule. This
must be distinguished from intermolecular hydrogen bonding, in which the attraction
is between a hydrogen atom and an electronegative atom on an adjacent molecule.

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Topic 1.4

PERIODICITY
The Periodic Table
Trends in Period 3
Trends in Group II

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THE PERIODIC TABLE

The periodic table is a list of all known elements arranged in order of increasing
atomic number, from 1 to 106. In addition to this, the elements are arranged in such
a way that atoms with the same number of shells are placed together, and atoms
with similar electronic configurations in the outer shell are also placed together. This
is achieved as follows:

The elements are arranged in rows and columns. Elements with one shell are
placed in the first row (ie H and He), Elements with two shells are placed in the
second row (Li to Ne) and so on.

A row of elements thus arranged is called a period.

In addition, the elements are aligned vertically (in columns) with other elements in
different rows, if they share a similar outer-shell electronic configuration. For
example, elements with outer-shell configuration ns1 are all placed in the same
column ( Li, Na, K, Rb, Cs, Fr).

A column of elements thus arranged is called a group.

According to these principles, the periodic table can be constructed as follows:

I II III IV V VI VII 0
H He

Li Be B C N O F Ne
Na Mg Al Si P S Cl Ar
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba La Ce - Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra Ac Th - Lw

Since the electronic configurations of H and He are unusual, they do not fit
comfortably into any group. They are thus allocated a group based on similarities in
physical and chemical properties with other members of the group.
He is placed in group 0 on this basis, but hydrogen does not behave like any other
element and so is placed in a group of its own.

The elements Ce - Lu and Th - Lw belong in the periodic table as shown above.

However if they are placed there periods 6 and 7 do not fit onto a page of A4, so
they are placed below the other elements in most tables.

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All elements belong to one of four main blocks: the s-block, the p-block, the d-block
and the f-block.

The s-block elements are all those with only s electrons in the outer shell.

The p-block elements are all those with at least one p-electron in the outer
shell.

The d-block elements are all those with at least one d-electron and at least
one s-electron but no f or p electrons in the outer shell.

The f-block elements are all those with at least one f-electron and at least one s-
electron but no d or p electrons in the outer shell.

I II III IV V VI VII 0
H He

Li Be B C N O F Ne
Na Mg Al Si P S Cl Ar
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba La Ce - Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra Ac Th - Lw

Elements coloured green are in the s-block

Elements coloured blue are in the p-block
Elements coloured red are in the d-block
Elements coloured black are in the f-block

The physical and chemical properties of elements in the Periodic Table show clear
patterns related to the position of each element in the Periodic Table. Elements in
the same group show similar properties, and properties change gradually on
crossing a Period.

As atomic number increases, the properties of the elements show trends which
repeat themselves in each Period of the Periodic Table. These trends are known
as Periodic Trends and the study of these trends in known as Periodicity.

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TRENDS IN PERIOD 3

Properties of individual atoms

a) Atomic size

On moving across Period 3 from left to right, the nuclear charge increases but the
shielding stays the same. The attraction of the outer electrons to the nucleus thus
increases and the outer electrons are pulled in closer. The size of the atoms just
decreases on crossing a period – i.e. sodium is the largest atom in Period 3 and
neon is the smallest.

Size of atoms of Period 3 elements

0.25

0.2
Na

0.15
Mg
Al
nm

Si
P
0.1 S Cl Ar

0.05

b) Ionization energies

Ionisation energy generally increases across period 3 but decreases between

groups II and III and also between groups V and VI.
Ionisation energy increases across period 3 because the nuclear charge increases
but the shielding remains the same, making the electrons harder to remove.
Ionisation energy decreases from group II to group III because the outer electron in
Al is in a 3p orbital, but the outer electron in Mg is in a 3s orbital. The 3p orbital is
better shielded from its nucleus making it easier to remove.
Ionisation energy decreases from group V to group VI because the outermost 3p
electron in S is paired, so there is repulsion in the orbital and the electron is easier
to remove. The outermost 3p electron in P is unpaired, so experiences less
repulsion and is harder to remove.
Ist ionisation energies of Period 3 elements

1800

1600
Ar
1400
Ionisation energy (kJ/mol)

Cl
1200

1000 P S

800 Si
Mg
600 Al
Na
400

200

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c) Electronegativity

Electronegativity increases across period 3. As the nuclear charge increases but

the shielding remains the same, the electrons are attracted more strongly to the
atom, so that atom will have a larger share of the electrons in a covalent bond.

Structure and Bonding

The structure and bonding of the elements in period 3 of the Periodic Table varies
widely.
There is a gradual decrease in metallic character in crossing a period.

On crossing a period the ionisation energies increase so it becomes more difficult to

remove electrons and form metallic structures. Thus covalent bonding becomes
more common on crossing a period from left to right.

The noble gases form neither metallic nor covalent bonds with each other. The
ionisation energies are very high so metallic bonding is not possible. There are no
unpaired electrons so covalent bonding is not possible. Thus they form no bonds
and exist as free gaseous atoms.

The trends in intramolecular bond type can be seen in the following table:

Na Mg Al Si P S Cl Ar
metallic metallic metallic covalent covalent covalent covalent -

The variation on bond type causes a number of differences in the structures of the
Period 3 elements which in turn causes significant differences in physical
properties.

a) Sodium, Magnesium and Aluminium

Sodium, Magnesium and Aluminium are metals. They consist of an infinite lattice of
cations held together by a sea of delocalised electrons. There is a fairly strong
attraction between the cations and the delocalised electrons and as a result metals
tend to have fairly high melting points and boiling points.

The melting points increase with increasing charge and decreasing size and thus
increase across a period.

Element Sodium Magnesium Aluminium

Mpt/oC 98 669 680
Bpt/oC 883 1107 2467

The delocalised electrons in the metal structure are free to move throughout the
metal lattice and can thus behave as charge carriers. When a potential difference is

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applied, the electrons can move towards the positive electrode. Thus metals are
good conductors of electricity.

Electrical conductivity increases from sodium to aluminium as the number of

delocalized electrons per atom increases. Aluminium has three electrons per atom
in the sea, magnesium two per atom and sodium only one per atom.

b) Silicon

Silicon is a giant covalent macromolecule. Silicon atoms form infinite lattices in

which all the atoms are held together by strong covalent bonds. Since the structure
cannot be broken up without breaking these strong covalent bonds, it follows that
silicon has a very high melting and boiling point. The structure of silicon is
tetrahedral, identical to diamond:

Structure
SILICON:

Mpt/oC 1406
Bpt/oC 2355

Silicon does not conduct electricity well as it has no free electrons and no free ions.

c) Phosphorus, sulphur, chlorine and argon

Phosphorus, sulphur, chlorine and argon form simple molecular structures.There

are strong, covalent bonds within the molecule but the different molecules are only
held together by weak Van der Waal's forces. Separating these molecules thus
requires little energy and the melting and boiling points of these elements are
relatively low.

The larger the molecule, the greater the magnitude of the temporary and induced
dipoles and the higher the melting and boiling points.

Melting points of P eriod 3 elements

1800
Si
1600

1400

1200

1000
Mg Al
800

600

400 Na S
P
200 Cl
Ar
0

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Element Phosphorus Sulphur Chlorine Argon

Structure

Mpt/oC 44 119 -101 -189

Bpt/oC 280 445 -35 -186
Formula P4 (or P) S8 (or S) Cl2 Ar

Sulphur has the highest melting point as it exists as S 8 molecules. These molecules
are quite large, so the number of electrons in the molecule is high and the Van der
Waal’s forces are quite strong. Phosphorus exists as P 4 molecules, which have
fewer electrons in them and so have weaker Van der Waal’s forces. So phosphorus
has a lower melting point than sulphur. Chlorine exists as molecules, which have
even fewer electrons in them so the Van der Waal’s forces are lower and chlorine
has a lower melting point than sulphur and phosphorus. Argon has the lowest
melting and boiling point of all, as it exists as single Ar atoms which have even less
electrons and so only form very weak Van der Waal’s forces.

These elements do not conduct electricity well as they have no free electrons and
no free ions.

Summary of properties of period 3 elements

 Atomic size – decreases across the period

 First ionization energy – increases across the period

 except between Mg and Al
 and between P and S

 Electronegativity – increases across the period

 Melting and boiling point – increases from Na to Al

– increases from Al to Si
– decreases from Si to P
– increases from P to S
– decreases from S to Ar

 Electrical conductivity – increases from Na to Al

– is zero from Si to Ar

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Element: Sodium Magnesium Aluminium Silicon Phosphorus Sulphur Chlorine Argon

(white)
Bonding: Metallic Metallic metallic covalent Covalent covalent covalent -

Structure:

Type: Metallic Metallic Metallic Giant Simple Simple Simple Simple

covalent molecular molecular molecular atomic
Melting 98 669 680 1410 44 119 -101 -189
point/oC:
Boiling 883 1107 2467 2355 280 445 -45 -186
point/oC:
First IE/ 496 738 578 789 1012 1000 1251 1521
kJmol-1:
E- 0.9 1.2 1.5 1.8 2.1 2.5 3.0 -
negativit
y
Electrical 0.21 0.26 0.41 0 0 0 0 0
conductiv
ity
(x10-8Ω-
1 -1
m )

NB You do not need to know the exact figures, just know the trends and be able to
explain them.

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Topic 1.5

INTRODUCTION TO ORGANIC CHEMISTRY

Introduction to Organic Chemistry
Nomenclature
Isomerism

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INTRODUCTION TO ORGANIC CHEMISTRY

Carbon compounds

Organic chemistry is the chemistry of carbon compounds. Carbon forms a vast

number of compounds because it can form strong covalent bonds with itself. This
enables it to form long chains (up to 5000 in length) of carbon atoms, and hence an
almost infinite variety of carbon compounds are known.
The tendency of identical atoms to form covalent bonds with each other and hence
form chains is known as catenation.

All organic compounds contain carbon. Most contain hydrogen.

Carbon always forms four covalent bonds and hydrogen one.

The physical and chemical properties of organic compounds depend on two

factors:

a) The number and arrangement of carbon atoms in the molecule.

A number of important physical properties are determined by the number of carbon

atoms in the molecule. The greater the number of carbon atoms, the larger the Van
der Waal’s forces and the higher the melting points, boiling points and viscosity.

In many cases, all the carbon atoms are arranged in a straight chain. Often,
however, there are shorter chains of carbon atoms branching off a longer chain.
These are known as branched molecules.

Straight chain molecule Branched molecule

Carbon atoms can also be arranged to form rings. These are known as cyclic
molecules. The most common number of carbon atoms in a ring is 6.

Cyclic molecule

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b) The functional groups in the molecule

A functional group is a specific atom or group of atoms which confer certain

physical and chemical properties onto the molecule. Organic molecules are
classified by the dominant functional group on the molecule.

Functional groups

These are the some of the most important functional groups found on organic
molecules:

Type of compound Nature of functional group

Alkane C-C and C-H single bonds only (ie no functional group)

Alkene C=C double bond

Haloalkane Cl, Br or I atom attached to a carbon atom

-Chloroalkane
-Bromoalkane
-Iodoalkane

Drawing and writing organic compounds

Organic compounds can be represented in a number of ways:

a) Structural formula showing all covalent bonds

This is also known as the displayed formula or graphical formula. All covalent
and ionic bonds between all atoms are shown:

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b) Structural formula, not showing all covalent bonds

Enough information is shown to make the structure clear, but most of the actual
covalent bonds are omitted. Only important bonds are always shown.

Straight chain alkanes are shown as follows:

is represented as CH3CH2CH2CH3 or CH3(CH2)2CH3.

Branched alkanes are shown as follows:

is represented as CH3CH(CH3)CH3.

is represented as CH3C(CH3)2CH3.

Alkenes are shown as follows:

is represented as CH2=CHCH3.

is represented as CH3CH=CHCH3.

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c) Molecular formula

The molecular formula shows the number of each atom in one molecule of the
compound. It does not show unequivocally the structure of the molecule.

is written C4H10

is written C4H8

Alkanes have the general molecular formula CnH2n+2.

Alkenes have the general molecular formula CnH2n.

Haloalkanes have the general molecular formula CnH2n+1X.

d) Empirical formula

The empirical formula is the simplest whole number ratio of the number of atoms of
each element in a substance.

Homologous series

Organic compounds with the same functional group, but a different number of
carbon atoms, are said to belong to the same homologous series. Every time a
carbon atom is added to the chain, two hydrogen atoms are also added.

A homologous series is a series of organic compounds which have the same

functional group, but in which the formula of each successive member
increases by -CH2-.

Eg Homologous series of alkanes:

CH4, CH3CH3, CH3CH2CH3, CH3CH2CH2CH3, CH3(CH2)3CH3, CH3(CH2)4CH3 etc

As a homologous series is ascended, the size of the molecule increases. Therefore

the Van der Waal’s forces between the molecules become stronger and the boiling
point increases.

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NOMENCLATURE OF ORGANIC COMPOUNDS

Most organic compounds can be named systematically by the IUPAC method.

In order to describe completely an organic molecule, three features must be

described:

- the longest straight carbon chain on the molecule.

- the length and position of any branches on the molecule.

- the nature and position of any functional groups on the molecule.

The longest straight chain on the molecule

The longest straight chain on the molecule is indicated by one of the following
prefixes:
Number of carbon atoms in the chain Prefix

1 Meth-
2 Eth-
3 Prop-
4 But-
5 Pent-
6 Hex-

The nature and position of any functional groups on the molecule

Alkanes

Alkanes are named using the ending -ane:

Methane

Ethane

Propane

Butane

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Alkenes

Alkenes are named using the ending -ene. In molecules with a straight chain of 4 or
more carbon atoms, the position of the C=C double bond must be specified. The
carbon atoms on the straight chain must be numbered, starting with the end closest
to
the double bond. The lowest-numbered carbon atom participating in the double
bond
is indicated just before the -ene:

Ethene

Propene

But-1-ene

But-2-ene

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Haloalkanes

Haloalkanes are named using the prefix chloro-, bromo- or iodo-, with the ending -
ane. In molecules with a straight chain of three or more carbon atoms, the position
of the halogen atom must also be specified. The carbon atoms on the straight chain
must be numbered, starting with the end closest to the halogen atom. The number
of the carbon atom attached to the halogen is indicated before the prefix:

Chloroethane

2-bromopropane

1-iodopentane

3-chloropentane

The position of all halogens in dihaloalkanes except those with one carbon atom
must be specified. If there is more than one of the same type of halogen atom on
the molecule, the di (two), tri (three) or tetra (four) prefixes must also be used.

1,1-dichloroethane

1,2-dichloroethane

1-bromo,2-chloropropane

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The length and position of any branches on the molecule

Many carbon chains are not, in fact straight but are branched. The presence of a
branch is indicated one of the following prefixes:

Branch Prefix

Methyl

Ethyl

The position of the branch must be specified according to the number of the carbon
on the straight chain to which it is attached. The carbons are always numbered from
the carbon at the end of the chain closest to the functional group. If there is no
functional group, the carbons are numbered from the carbon at the end of the chain
closest to the branch.

Eg

2-methylbutane 2,2-dimethylpropane

2-methyl,3-ethylpentane 3,3-diethylpentane

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2-methyl,2-chloropropane 2-methyl,1-chloropropane

Many organic compounds which appear to be different are in fact the same. They
appear to be different because different notations are used, or because some of the
bonds are simply rotated.

Eg butane can be represented in a number of ways:

Such as

Eg 1-chloropropane can be represented in a number of ways:

Such as

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ISOMERISM

Isomers are molecules which have the same molecular formula but different
structures.

There are a number of different types of isomerism in organic compounds, but the
only type required for AS Chemistry is structural isomerism.

Structural isomers are molecules which have the same molecular formula but
a different arrangement of covalent bonds.

The different arrangement of covalent bonds can result from:

i) The functional group being in different positions (positional isomerism)
ii) A different arrangement of the carbon skeleton (chain isomerism)
iii) A different functional group (functional isomerism)

i) Positional isomerism

Positional isomers are molecules with the same molecular formula but which
have the functional group on different positions in the molecule.

Alkanes do not show functional isomerism as they have no functional group.

Alkenes with four or more carbon atoms show positional isomerism:

Eg but-1-ene and but-2-ene

Haloalkanes with three or more carbon atoms show positional isomerism

Eg 1-chloromethylpropane and 2-chloromethylpropane

ii) Chain isomerism

Chain isomers are molecules with the same molecular formula but a different
arrangement of carbon atoms.

The arrangement of carbon atoms in an organic molecule is known as the carbon

skeleton.

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Carbon skeletons containing up to three carbon atoms can only be arranged in one
way – i.e. a straight chain with no branching:

Carbon skeletons containing four carbon atoms can be arranged in two ways:

Carbon skeletons containing five carbon atoms can be arranged in three ways:

Carbon skeletons containing six carbon atoms can be arranged in five ways:

All molecules containing four or more carbon atoms can thus show chain
isomerism:

Eg. Butane and methylpropane

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Eg. pent-1-ene and 2-methylbut-1-ene

Eg. 1-chloropentane and 1-chloro,2,2-dimethylpropane

iii) Functional isomerism

Functional isomers are molecules with the same molecular formula but
different functional groups.

eg Alkanes which have a ring rather than a straight chain arrangement are
known as cycloalkanes. They have the general formula C nH2n, which is the
same as alkenes. Cycloalkanes and alkenes can thus show functional
isomerism.

Eg cyclohexane and hex-1-ene

Eg cyclobutane and but-1-ene

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3. Distinguishing between isomers

Isomers tend to differ slightly in their melting and boiling points. Molecules with no
branching tend to have higher boiling points than isomers with more branching. This
is because they have a higher surface area, so they pack together better and so the
van der Waal’s forces are stronger.

Eg isomers of pentane, C5H12:

Isomer Structure Boiling point/oC

Pentane

36

Methylbutane

28

2,2-dimethylpropane

10

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Topic 1.6

PETROLEUM AND ALKANES

Fractional Distillation
Cracking
Combustion

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CRUDE OIL

1. Introduction

The vast majority of carbon-containing compounds in widespread use have been

made from crude oil. Crude oil is also known as petroleum.

Crude oil is a mixture of hydrocarbons. A hydrocarbon is a substance

containing carbon and hydrogen only. Most of the hydrocarbons in crude oil are
alkanes. Alkanes are hydrocarbons containing only single bonds between the
carbon atoms.

Each of the hydrocarbons present in crude oil has a slightly different use. Mixed
together they are of no use at all. It is necessary, therefore, to separate them before
they can be used productively. Crude oil is separated into its different components
by a process called fractional distillation.

The products of fractional distillation are often converted into other, even more
useful hydrocarbons by a process called cracking.

2. Fractional distillation

The different hydrocarbons in crude oil have different boiling points. This is because
the chain length varies. The greater the number of carbon atoms in the chain, the
longer the chain length. This results in more Van der Waal’s forces acting between
the molecules and a greater intermolecular attraction. Thus more energy is needed
to separate the molecules and the boiling point is higher. It is the difference in
boiling points of the different hydrocarbons in crude oil which is used to separate
them from each other.

The crude oil is passed into a tall tower called a fractionating column. This is very
hot near the base but much cooler near the top. When the crude oil is passed into
the tower, near the bottom, most of the mixture boils and starts to rise up the tower.
As they rise up the tower, they start to cool down and will gradually condense back
into liquid form. They are then tapped off. The larger hydrocarbons, with higher
boiling points, will condense first and be tapped off near the base of the column.
The smaller hydrocarbons, with smaller boiling points, will condense later and be
tapped off near the top of the column. Thus the separation is achieved. Not that the
process involves breaking intermolecular forces only; the molecules themselves
are unaffected by this process.

This process does not actually separate the crude oil mixture into pure hydrocarbon
components, but into mixtures called fractions. Fractions are mixtures of
hydrocarbons with similar boiling points. In many cases these fractions can be
used directly, but sometimes further separation is required into purer components.

The following page shows a diagram of a typical fractionating column, and a table
showing the most important fractions and their main uses:

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A fractionating column

Fractions from crude oil

Name of fraction Boiling range Number of Uses

/ oC hydrocarbons
Liquefied petroleum gas Less than 25 1–4 Gas for camping/ cooking
Petrol or gasoline Fuel for cars etc
Naphtha Petrochemicals
Kerosine or paraffin Plane fuel, petrochemicals
Diesel or gas oil lorry, central heating fuel
Mineral/lubricating oil Lubrication, petrochemicals
Fuel oil Ship fuel, power stations
Wax and grease Candles, grease, polish
Bitumen or tar Road surfaces, roofing

Above 450 More than 50

The term petrochemical means that the compounds are converted into other
chemicals for use as solvents, paints and various other things.

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3. Cracking

Although all of the fractions produced from crude oil have their uses, some of the
fractions are produced in greater quantities than needed, whilst others are not
produced in sufficient quantities. The table below gives an example of the
difference between the supply and demand of some important fractions:

Supply and demand for fractions

Fraction Approximate supply/% Approximate demand/%

Liquefied petroleum gases 2 4
Petrol and naphtha 16 27
Kerosine 13 8
Gas oil 19 23
Fuel oil and bitumen 50 38

This disparity can be corrected by breaking up some larger hydrocarbons in fuel oil
into the smaller ones found in gas oil, or by breaking up some hydrocarbons in
kerosene into the smaller ones found in petrol, naphtha or the liquefied petroleum
gases. In other words the larger fractions (for which supply exceeds demand) can
be broken up into smaller fractions (for which demand exceeds supply).

The process by which this is carried out is called cracking.

Cracking has the added advantage of producing other useful hydrocarbons not
naturally present in crude oil, such as alkenes (widely used as petrochemicals),
cycloalkanes and branched alkanes (widely used in motor fuels) and aromatic
hydrocarbons (used as petrochemicals and as motor fuels).

Thus cracking is important for two reasons:

i) It converts low-demand fractions into higher demand fractions
ii) It makes useful hydrocarbons not naturally found in crude oil

There are two types of cracking: thermal cracking and catalytic cracking. Both
involve the breaking of C-C bonds to form smaller molecules. C-C bonds are
weaker than C-H bonds and so break more easily when heated.

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a) Thermal cracking

In thermal cracking, the bonds are broken using a high temperature (400 – 900oC)
and a high pressure (70 atmospheres).

The high temperatures mean that the molecule breaks near the end of the chain,
giving a high percentage of small alkenes such as ethene.

Most thermal cracking reactions involve the formation of one of more small alkane
molecules and one alkene molecule. Naphtha (C7 – C14) is usually used as the
starting material.

Eg C8H18  C6H14 + C2H4

Eg C6H14  C3H8 + C3H6

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b) Catalytic cracking

In catalytic cracking, the bonds are broken using a high temperature (450 oC,
which is generally lower than in thermal cracking), a slight pressure (slightly
greater than 1 atmosphere), and a zeolite catalyst.

Catalytic cracking is cheaper and more efficient than thermal cracking as it uses a
lower temperature and pressure.

The zeolite catalyst favours the formation of branched alkanes and cycloalkanes,
which are widely used in motor fuels. The most important product of catalytic
cracking is 2-methylheptane, which is the major component of petrol. It also
produces aromatic hydrocarbons such as benzene, which have a variety of uses.

Eg

A table summarising the differences between thermal and catalytic cracking can is
shown below:

Type of cracking Thermal Catalytic

Conditions High temperature (400 – 900 High temperature (450 oC)

o
C)
High pressure (70 atm) Slight pressure ( > 1 atm)

Zeolite catalyst

Main products High percentage of alkenes Motor fuels (ie branched

alkanes)

Aromatic hydrocarbons

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COMBUSTION OF ALKANES

Alkanes as Fuels

Many of the fractions produced from crude oil are used as fuels. These fractions
include:

Fraction Uses

Liquefied petroleum gases Camping gas, cooking gas

Petrol Fuel for cars, motorbikes and machines

Kerosine Fuel for aeroplanes, lamps, ovens

Diesel Fuel for lorries, and central heating systems

Fuel oil Fuel for ships, power stations

Wax Fuel for candles

A fuel is a something that can be changed in a reacting vessel to produce useful

energy.

Hydrocarbons, and especially alkanes, will react with oxygen in the air to give
carbon dioxide and water. A reaction with oxygen is known as combustion. As
alkanes are unreactive the reaction needs heat or a spark to get going.

These reactions are very exothermic, which means that heat energy is released.
This heat energy can be used for direct heating (eg camping gas, central heating,
candles). It can also be converted into mechanical energy (eg cars, lorries, ships),
or even electrical energy (eg power stations).

Typical examples of combustion reactions include:

Reaction Enthalpy change/ kJmol-1

CH4 + 2O2  CO2 + 2H2O -890

C4H10 + 6½O2  4CO2 + 5H2O -2877
C8H18+ 12½O2  8CO2 + 9H2O -5470

The release of heat energy during these combustion reactions results in their
widespread use as fuels.

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Pollution problems associated with burning hydrocarbons

a) Carbon dioxide

Although carbon dioxide is not poisonous and is naturally removed from the
atmosphere by plants, the enormous quantities of hydrocarbons burned in recent
years has caused carbon dioxide levels to rise significantly.

Carbon dioxide, along with various other compounds, prevents the earth’s heat
from escaping into space and is resulting in an increase in the earth’s temperature.
This is known as global warming. The result is the melting of the polar ice caps
which is likely to cause severe flooding in the future, as well as serious damage to
numerous ecosystems.

Gases which contribute towards global warming are known as greenhouse gases.

b) Water vapour

Water vapour is also produced in large quantities as a result of combustion of

hydrocarbons and is also a greenhouse gas.

c) Carbon monoxide and carbon

The combustion of hydrocarbons to produce carbon dioxide and water is called

complete combustion, and it requires a lot of oxygen. If oxygen is not present in
sufficiently large quantities, carbon monoxide or carbon is produced instead of
carbon dioxide. This is called incomplete combustion.

Examples of incomplete combustion reactions are:

C4H10 + 4½O2  4CO + 5H2O Incomplete combustion

C4H10 + 2½O2  4C + 5H2O Incomplete combustion
C8H18+ 10½O2  8CO + 9H2O Incomplete combustion
C8H18+ 8½O2  8C + 9H2O Incomplete combustion

The less oxygen that is available, the more likely it is that incomplete combustion
will occur. This is a particular problem in internal combustion engines where the air
supply is limited. Incomplete combustion is a problem for three reasons:

i) Less energy is released by incomplete combustion than by complete

combustion.
ii) Carbon monoxide is a pollutant – it is absorbed by the blood in place of
oxygen, and hence reduces the ability of the blood to carry oxygen
causing suffocation and eventually death.
iii) Carbon particles can cause breathing difficulties and cancer.

It is therefore desirable to ensure that the air supply is as good as possible when
burning hydrocarbon fuels.

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Occasionally incomplete combustion is desirable – such as with a Bunsen burner.

Closing the air hole produces a yellow flame (the yellow colour results from hot
carbon particles) and this makes the flame more visible and causes a more gentle
heat. Usually, however, complete combustion is considered more desirable.

d) Sulphur dioxide

Most crude oil deposits contain sulphur as an impurity. Oil refineries are
increasingly treating the petrol fractions to lower the sulphur content, but some
sulphur is still present in most hydrocarbon fuels. When the fuel is burned, the
sulphur also burns, producing sulphur dioxide:

S(s) + O 2(g)  SO2(g)

This gas dissolves in rainwater forming a very acidic solution, known as acid rain.
This causes various problems, including erosion of buildings and statues, killing of
plants and trees, and killing of fish through contamination of lakes.

e) Oxides of nitrogen

Most fuels are not burned in pure oxygen but in air, which contains 80% nitrogen.
Although nitrogen is not a reactive gas, the high temperatures and the spark in
combustion engines cause some of the nitrogen to react with the oxygen to produce
nitric oxide and nitrogen dioxide:

N 2(g) + O2(g)  2NO(g)

2NO(g) + O 2(g)  2NO2(g)

Nitrogen dioxide (NO2) also dissolves in rainwater to form an acidic solution and
contributes to the problem of acid rain.

Nitrogen oxides can also combine with unburned hydrocarbons to produce a

photochemical smog.

f) Unburned hydrocarbons

Some of the hydrocarbon fuel is vaporised in the engine but escapes before it is
burned. These unburned hydrocarbons cause various problems. They are toxic and
can cause cancer if breathed in.

They also combine with oxides of nitrogen to produce a photochemical smog.

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Ways of reducing pollution levels

A number of ways have been developed to reduce the polluting effects associated
with the burning of fossil fuels. Two examples are given here:

a) Flue gas desulphurisation

Many factory chimneys contain alkaline materials such as lime (calcium oxide).
These absorb the acidic gases such as SO2 and thus prevent them from escaping:
SO2 + CaO  CaSO3

Further reactions result in the formation of CaSO 4 (gypsum) which is used to make
plaster.

b) Catalytic Converters

Most modern car exhausts are now fitted with catalytic converters. These are
designed to convert some of the more harmful gases present in car exhausts into
less harmful ones. Unburned hydrocarbons, carbon monoxide and the oxides of
nitrogen can all be converted into less harmful gases inside these converters.

There are two main types of reaction taking place in a catalytic converter:

i) Removal of carbon monoxide and nitrogen monoxide

2NO(g) + 2CO(g)  N2(g) + 2CO2(g)

Hence harmful NO and CO gases are converted into the less harmful nitrogen and
carbon dioxide.

ii) Removal of unburned hydrocarbons and nitrogen monoxide

eg. C8H18 + 25NO  8CO2 + 9H2O + 12.5N2

Hence harmful unburned hydrocarbons and oxides of nitrogen are converted into
the less harmful carbon dioxide, water and nitrogen.

The reality is, however, that the burning of hydrocarbon fuels has caused and
continues to worsen most of the planet’s most serious environmental problems.
Although technological innovations such as catalytic converters can limit some of
the damage, the only action which will have any lasting effect is to reduce the
reliance of rich Western countries, especially the USA, on fossil fuels. This will only
happen if the potential of alternative sources of energy is more fully exploited, the
political and economic power of oil barons is curbed and wealthy industrialised
countries look at ways to reduce their energy consumption. Achieving these goals,
however, has been socially and politically problematic.

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