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Foundation Chemistry (Lectures 1-3)

Prof. G. Williams (Room A231, Engineering East)


Chemistry : the study of matter and the interactions between different types of matter.
Question; why don’t we make cars from Caesium?
Why do potential engineers need a knowledge of chemistry
When we make an object for a certain purpose we must chose a suitable material; but what dictates what materials are
suitable for different tasks. A range of metals are used for various engineering applications. Aluminium is an example
of a light metal which is strong and can be used in airframes. Iron is a material suitable for many structural applications
but it is heavier and can suffer from corrosion. Polymers can be made from crude oil based on the elements carbon and
hydrogen. Glasses can be made from sand and many building materials can be made from rocks. All materials are
made from elements or combinations of elements. But why can’t we use elements like Caesium (which can be
lightweight) for structural applications and why is it that iron corrodes whereas metals like titanium and aluminium do
not? Why can’t we make hydrocarbon like polymers from other non metals like sulphur (S) and silicon (Si). Why does
the universally useful material limestone comprise the elements Calcium, carbon and oxygen in the ratio that it does
(CaCO3)
Elements and Alchemy
The ancient Greeks thought that materials were made of four basic components, earth, fire, air and water; these were
known as elements. They believed that all the materials available on the Earth were made from these basic elements
and therefore that materials could be easily converted from one form to another.

This lead to extensive research by early scientists into the subject of Alchemy; the science of turning base things into
gold. Surely if all materials were made out of four basic elements it should be possible to blend materials together and
make new material. This is of course true to a certain extent but unfortunately most Alchemists obtained at best
samples of purest Green (ref BlackAdder!)
These ideas on the composition of matter is not so daft though. Scientists later began to find out that there were pure
materials that could not be broken down, such as gold. These were termed elements. In fact there are many chemical
elements (currently 105) and all the materials that we use are indeed made from them. Unfortunately Gold is one of
those elements and so the Alchemists dreams were shattered when it was realised that it was a pure element and it could
not be made with magic spells and bubbling pots!!

Sources of Elements
The Big Bang heralded the beginning of the Universe some 15-20 billion years ago and at the instant the universe
formed two elements, hydrogen and helium, were present. These gases condensed and formed into galaxies and stars.
As we have seen these elements dominate the overall Universal composition.

UNIVERSE EARTH’S CRUST


silicon 15.2%
magnesium 12.7%
nickel 2.4%
sulphur 1.9%
oxygen 29.5% others 3.5%%

iron 34.6%

(b) EARTH (OVERALL)

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Fortunately for us things did not stay like this. Due to the intense physical conditions inside stars fusion reactions
occurred in which atoms combined and new heavier elements were created. Around the stars heavy elements formed by
fusion reactions began combining together and the first planets were born. Overall the universe is still mostly made up
of hydrogen and helium. The Earth has a very different composition (see above); notice how the overall and crustal
compositions are very different to each other and to the universal composition.

The elemental fusion reactions inside stars have lead to the formation of a wide array of elements with different
properties and they can react together to form a variety of compounds.

Atoms; what elements are made of


Definition: An atom is the smallest part of an element that can ever exist. All elements are made up of atoms. The atom
comprises a nucleus that can contain positively charged protons and neutral neutrons and surrounding that clouds of
negatively charged electrons; the number of protons, neutrons and electrons present determines the element you are
looking at. The clouds of electrons are responsible for the chemical properties of the elements and also dictate the ways
that atoms bind together. In other words they also control the compounds that elements form with each other. The
electrons are built up in shells of discrete energy around the nucleus. The electrons in shells closest to the nucleus are
most strongly held (they are closest to the positive charge!).

Example Sodium Nucleus: 11 protons


Atomic number 11 12 neutrons
11 electrons

The basic properties of materials are controlled by their chemistry. What makes materials good and bad for certain uses
depends almost entirely on their chemical properties. We have said we would not make a car or aeroplane from
caesium, but why??

One of the problems which we have when designing materials is that there are 105 elements; where do we go to decide
what elements will do what and which will be suitable for our purpose? This was a situation that faced scientists and
engineers over a hundred years ago

History Today; The Origins of the Periodic Table


you see those elements those are your best elements

By the 19th century 50 elements had been discovered and isolated. Chemists were increasingly trapped in a
bewildering sea of materials with different properties and it was becoming increasingly important to try and cut down
the amounts of information that was being generated. The problem was that all the elements were a bit like pieces in a
Jigsaw puzzle. This was a puzzle with missing instructions, missing parts and some pieces that had been cut to the
wrong shape.

One of the greatest discoveries was made by John Dalton who suggested that each element was made up of atoms and
that the atoms for an element were identical to one another and differed to atoms of other elements in their mass; this
was the idea of atomic mass. Very soon scientists had made measurements on the atomic masses of all the known
elements.

In 1829 a real breakthrough was made by a German scientist Doberenier who noticed that the elements Calcium
Strontium and Barium behaved in very similar ways. They all burned with bright coloured flames for instance (which
is why they are often used in fireworks); he also noticed that the atomic masses followed a an approximate pattern
aswell (atomic masses 40 88 137). He also noticed chlorine, bromine and iodine had similar properties and again had
similar patterns in the atomic masses 35 80 127. He called these groups Triads but most scientists of the day believed
it was little more than an interesting coincidence.

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Döbereiner’s triad of alkali metals Döbereiner’s triad of halogens

By 1864 there were now 63 elements. John Newlands suggested there was a link between Atomic Masses and chemical
properties; he again noticed regular occurrence of some properties of the metals. For example Lithium Li, and Sodium
Na, had very similar physical properties (they are all soft metals that are easily cut with a knife) and have similar
reactions (eg violent reaction with water) Newlands ordered the elements in rows of 8 in increasing atomic mass such
that the elements he believed were similar to one another were above each other in a table. These were known as
Newlands octaves.

Newlands’ octaves
H Li Be B C N O
F Na Mg Al Si P S
Cl K Ca Cr Ti Mn Fe
Co and Ni Cu Zn Y In As Se
Br Rb Sr Ce and La Zr Di and Mo Ro and Ru
The problem lay in the way the elements were ordered; when ordered simply in terms of atomic mass the element
copper (Cu) was in the same group as sodium and lithium and showed no similarities in behaviour. Indeed the patterns
were only really visible in the first fifteen elements and so scientists rejected the idea saying that the elements might as
well be organised alphabetically or in terms of colour!!

Group Group Group Group Group Group Group Group


I II III IV V VI VII VII
Period 1 H
Period 2 Li Be B C N O F
Period 3 Na Mg Al Si P S Cl
Period 4 K Ca * Ti V Cr Mn Fe Co Ni
Cu Zn * * As Se Br
Period 5 Rb Sr Y Zr Nb Mo * Ru Rh
Ag Cd In Sn Sb Te I Pd

The greatest breakthrough as when the Russian Scientist Dmitri Ivanovic Mendeleev decided in 1869 to order elements
in order of atomic mass but swap some elements according to their chemistry (he cheated). He also realised that there
might be undiscovered elements. He produced a Periodic table with blanks in it left for undiscovered elements. His
ideas were vindicated by the discovery of Germanium in 1885 for which Mendeleev had correctly predicted its
chemical properties.

There were still some problems though since scientists were worried about the idea of simply ignoring atomic masses.
The final breakthrough came when Henry Moseley in the early 20th century looked at the Xrays given off by atoms.
This gave rise to information of the number of electrons surrounding each atom. This was termed the atomic number
and when the elements were ordered in order of their atomic number the problems of mass disappeared and the
elements were correctly ordered as Mendeleev had predicted.

Modern Day Alchemy


The story does not end there; there are 92 naturally occurring elements on Earth ending in Uranium. With the discovery
and exploitation of nuclear power and the creation of weapons of mass destruction such as hydrogen bombs new
elements have been synthesised which have never existed on Earth before. This is true alchemy although the traditional
alchemist

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All an alchemist needs is an H bomb and a small Australian atoll!!!

The Modern Periodic Table


The modern Periodic Table is shown below and it is an extraordinarily powerful tool to quickly scan materials
suitability and elemental reactivity.

Atomic Number, Atomic Mass and Isotopes


The periodic table lists elements in order of their atomic number (Z). This is the number of protons in the nucleus or
the number of electrons circulating it.
Listed in the periodic table is also the atomic mass (Ar); this is a number of protons and neutrons in the nucleus
expressed in grammes. You will notice that most of these numbers are not whole numbers. This is due to the
phenomenon known as isotopes. Isotopes have the same number of protons and electrons but differing numbers of
neutrons.

Measuring atomic mass accurately: A mass spectrometer

This is an accurate method of determining atomic masses by finding the relative abundance of isotopes of the element
under consideration.
5 operations are performed by the mass spectrometer
i. The sample is vapourised
ii. Positive ions are produced from the vapour by bombardment with an electron beam

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3. Ions are accelerated by a known electric field
4. Ions are deflected by a known magnetic field
5. Ions are detected
Volatile samples are introduced to the instrument by injection into the ionisation chamber. Involatile solids are
vapourised by pre-heating. The mass spectrometer is held under vacuum. In the ionisation chamber the bombardment of
the vapourised sample by a stream of electrons produces positive ions (on collision with the vapourised atoms, the
electron stream can knock out outer shell electrons).
e- + X  X+ + e- + e-
high-energy sample positive electron knocked retreating high-energy
electron atom ion out of X electron

The positive ions (X+) pass through holes in 2 parallel plates to which an electric field is applied, which accelerates the
ions towards the magnetic field. The ion stream then pass through a magnetic field and are deflected according to their
mass. When a constant magnetic and electric fields are applied only ions with one particular mass will be deflected to
the ion detector. Lighter ions will be deflected the most and vice-versa. Therefore by gradually increasing either the
magnetic field or the electric field (where faster isotopes are deflected least), ions of different masses are brought to the
detector.
Masses can be calculated from the known applied fields, but in practice the instrument is calibrated with a known
standard and relative masses of other ions are obtained by comparison. The relative size of the detector currents (or
relative height of peaks) gives the relative abundance or amount of the different ions present.

vacuum pump
Ionisation chamber

+ Heavier particles
X+

e-

Vapourised 0 -
sample
lighter particles

Electron gun

Accelerating Electromagnet
electric field

Detector
Examples carbon has an atomic number of 6 this means it has six protons in the nucleus and 6 electrons around the
nucleus (more later). There are two isotopes one with atomic mass 12 (6 protons and 6 neutrons) and one with an
atomic number 13 (6 protons and 7 neutrons). The overall atomic mass is 12.011. This is because 99% of carbon atoms
are of the 12 atomic mass variety and 1% are of atomic mass 13.

Another example is chlorine Cl; what is the atomic number?...................

What is the atomic mass of chlorine? ....................................

Chlorine has two isotopes one of mass 35 and one of mass 37. How many protons and neutrons are in the nucleus in
each case?? Here 75% is of isotope 35 and 25% is of isotope 37.
………………………………………………………………………………………………………………………………
……………………………………………………………………………………………………………………………..
Calculate Ar for Mg if its isotope composition is as follows 24Mg (78.6%), 25Mg (10.1%), 26Mg (11.3%).
………………………………………………………………………………………………………………………………
………………………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………………….
………………………………………………………………………………………………………………………….

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Patterns in the periodic table;
The Periodic table is an important way of classifying elements into groups that behave in similar or predictable ways.
Metals, Non-metals and metalloids
The simplest classification is to split the periodic table into metals, and non metals. There is a third group of materials
(the metalloids) that make up the boundary between the two.

Metals; metals are typically lustrous solid materials which conduct electricity and have quite high melting points. They
have a giant metallic structure and often act as reducing agents in reactions.

Non-metals; these are typically poor solids liquids or gases having a discrete molecular structure which do not conduct
electricity and generally have low melting points

Metalloids; these have characteristics between the metals and non metals being reasonable strong solid materials with a
Giant molecular structure which are neither conductors or insulators and have very high melting points. These
materials are infact semiconductors which are a very important class of materials.

This is a very crude classification since it is obvious that different metals will behave differently to one another but it
does allow us to see potentially what elements will do what.

Exercise; Classify the following elements as metal, metalloid or non metal.


Nitrogen N ............................... Radon Rn ...............................
Silicon Si ............................... Astatine At ...............................
Germanium Ge .............................. Scandium Sc ...............................
Niobium Nb ............................... Iodine I . ...............................
Antimony Sb ............................... Osmium Os ...............................

Although most chemical symbols for the elements are logical abbreviations of their names (e.g carbon (C), aluminium
(Al) etc), you will have noticed that many of the elements have some unusual notations for their symbol which stems
from their original Latin and Greek names. Examples: Lead, iron, silver –

Groups in the Periodic Table


Groups in the periodic table are arranged vertically. For example group 1 consists the elements Lithium Li, sodium Na,
potassium K, rubidium Rb, caesium Cs and francium Fr

Groups of elements have similar properties and definite patterns. The elements within groups have very similar
properties since the properties are due to the number outer shell electrons (see later). A group 1 element will have 1
outer shell electron, a group 2 element 2 electrons and so on. It is the outer electrons that control the chemical
properties of the elements and as we shall see the bonding to other atoms and so it is hardly surprising that elements
within groups have similar properties.
Group 1 metals reacting with water
All the group 1 metals undergo the following reaction forming a metal hydroxide and hydrogen gas:
2M + 2H2O  2M(OH) + H2
Down the group there is an increase in the intensity of reaction such that caesium explodes violently. This pattern is
also observed for other reactions of these metals such as burning, corrosion and so on. That is because these reactions
involve oxidation of the metal (to form an M + ion by losing 1 electron) and oxidation becomes easier as you move down
the groups.
M  M+ + e
This then allows us to predict that using caesium in any situation involving water would be extremely stupid. A similar
trend in increasing activity is observed in group 2 as well. Thus whereas we might use magnesium (with care!) in an
aircraft airframe we would not be able to use the element Strontium (Sr) which is below it in the table!

A strontium alloyed Jaguar fighter? I think not !!

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Patterns; noble gases of group 8
The noble gases are highly unreactive since they have full outer shells of 8 electrons. Down the group the density
increases such that neon (Ne) balloons rise upward but Xenon (Xe) filled balloons rapidly sink, but why? This all has
to do with atomic density. Down groups atoms are getting much heavier so the density of elements increases.

Groups of similar elements in the Periodic Table

Groups 1 (1 outer shell electron) and 2 (2 outer shell electrons) contain reactive metals like sodium, calcium and
magnesium which can be used as metals but also in chemical reactions to produce other useful materials (limestone for
instance!!)

Group 3 (3 outer shell electrons) contains metals the most important of which is aluminium although gallium is
important in electronics.

The transition metals are generally unreactive but are structurally strong; they have diverse uses from industrial and
automotive catalysts to making rigid structural metals and alloys.

Group 4 (4 outer shell electrons) contains an important transition from non metal (carbon) to metal lead (Pb); the
element carbon is exceedingly important for life on Earth, oils and petrochemicals and the polymers industry.

Group 5 (5 outer shell electrons) and 6 (6 outer shell electrons) contain important non metals like oxygen and sulphur
as well as nitrogen which are important industrial and biological materials

Group 7 (7 outer shell electrons) contains the elements known as the halogens; these are important oxidising agents and
are also important as constituents of salts as well as atoms for modifying polymer properties.

Group 8 (8 outer shell electrons) contains the noble gases; These are highly unreactive molecules and they are
important as chemical shields during processes such as welding where there inert nature protects metals being heated
very violently from the effects of reaction with the components of air (nitrogen and oxygen)

Periodic Patterns
Periods of elements occur in horizontal rows; there are again trends in activity. The most simple trend is that from
metal to non metal. There are also patterns in the chemical properties for example in forming oxides there is a definite
trend in the formulae of the oxides formed

Na2O MgO Al2O3 SiO2 P2O5 SO2 ClO formula of the oxide
0.5 1 1.5 2 2.5 2 1 number of oxygens per atom in oxide
This pattern is repeated from row to row in the periodic table. This combined with knowledge of the properties of
groups of elements allows us to use the table predictively to say what we believe is occurring during chemical reactions
and to predict whether particular materials will be suitable for particular tasks.

There is also an important trend in the ferocity of reaction; whilst sodium burns very vigorously in oxygen and forms
the oxide aluminium burns only as a powder which is important considering the uses we put this metal to in aeroplane
structures and car engines; but why does the metal become more stable in moving from group 1 to group 3? That is
because it becomes more difficult to oxidise the elements as you move to increasing group numbers.

Aims of the Course

During this course we will explore the properties of these elements and the compounds they make and try and relate
these to their performance as engineering materials.

The knowledge of chemical properties enables engineers to make better materials selection and allows greater
understanding of materials properties and performance.

Answer to question on Page 1: because they would explode on exposure to moisture!

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Electronic Structure and Bonding; Holding Materials Together

Structure of the Atom


Last time we saw that all elements were made up of atoms and that the atoms comprised a nucleus containing protons
and neutrons (giving the element its mass) and clouds or shells of electrons of different energies surrounding the
nucleus. The electron energies are said to be quantised (they have specific energy) and the electrons are described by
quantum numbers which tell you their energy and position from the nucleus These electrons are responsible for most of
the chemical properties of materials. How are these electrons arranged around the nucleus; we said last time that the
group number told you how many outer electrons there were, but how do we know this?

Ionisation energy
The ionisation energy of an atom is the amount of energy required to remove an electron from the atom and create an
ion.
M  M+ + e

In atoms with more than one electron it is possible to remove further electrons by further input of energy

M+  M2+ + e M2+  M3+ + e

and so on until all the electrons are removed. The electrons will become more and more difficult to remove since they
are closer to the nucleus and more strongly attracted.

Thus if we look at the pattern in the successive ionisation energy of atoms we can determine the energy of the electrons
in the orbitals around the nucleus. This gives us important information on the electronic structure of the atom which in
turn can be used to explain the bonding and chemical properties.

Lets look at the element sodium (atomic number 11)

There is one electron that is relatively easy to remove. This must be far away from the nucleus. Then there are a series
of 8 electrons of similar energy which must be closer to the nucleus. Finally there are two very strongly bound
electrons very close to the nucleus. It appears that there are three shells of electrons in sodium; the first with 2 electrons
the second with 8 and the outer most one with only 1 giving a total of 11 as predicted from the atomic number.

If we look at the next element in the period magnesium (atomic number 12) we now find two easily removed electrons

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Example (i) Predict the Ionisation Energy pattern for aluminium atomic number 13

(ii) Using the sketch below predict the electronic structure of the element oxygen

Measuring the ionisation energy of an atom


There are several ways of measuring the ionisation energy of atoms:
1 Gases bombarded with high energy
electrons
The ionisation energy of gases is easily
obtained using the apparatus shown.
Electrons are emitted from the heated
cathode and their kinetic energy depends
on the potential difference between the
plates. The gas of interest, G, fills the void
between the plates. When the kinetic
energy of the electrons is high enough they
are able to knock electrons straight out of
the atoms and make ions.
G + high energy e = G+ + 2e

There are now twice as many electrons around so the current between the plates doubles! The process is repeated as
more and more electrons are knocked out. Can only be used for gases. Some difficulty in removing all the electrons!

2 Atomic emission spectra;


When elements are vigorously heated in a high temperature flame many of them give of coloured light. For example
sodium (orange), potassium (red), strontium (crimson), copper (green) which are often used in fireworks. What is going

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on here? The electrons from lower levels are excited to higher levels by absorption of energy from an electrical
discharge and when they drop back down light is emitted.

E = hv = hc/

(E is the energy change, h = Planck constant, v the frequency of radiation, c the speed of light and  the wavelelength)

The light is not of a continuous band of frequencies but moreover a series of well defined lines corresponding to the
energy differences between the orbitals. These lines can be seen if the radiation is passed through a prism and split into
its component wavelengths. the separate lines indicate transitions between certain energy levels in the atom.

Consider hydrogen atoms which have only one electron. The series of lines illustrated above get closer and closer
together as the orbitals get further from the nucleus. Eventually the gap is negligible and any further energy input
would create an ion rather than excite the atom. This is the convergence limit and by plotting the energy of the light
emitted against a measure of the energy level change the ionisation energy can be measured.

The only problem with the technique is that the results can be difficult to interpret when many electron atoms are used.
Many atoms do not emit coloured light since the energy changes are too large and the wavelengths of light are in the
ultraviolet or far UV range.

3 Xray photoelectron spectroscopy; XPES


In this technique the atoms are bombarded with high energy X-rays (energy E) and these can knock out electrons. The
electrons acquire a kinetic energy k the size of which depends on the binding energy of the electrons B.
B = E - k

The binding energy of an electron is directly related to its ionisation energy. Thus by measuring the binding energy for
different atoms the electronic structure can be elucidated.
This is a very powerful technique which can not only be used to identify electronic structures but also identify the
atomic composition of materials (using known data fro electron energies). It is often combined as a probe within the
scanning electron microscope to enable elemental identification of objects under view.

Principal quantum numbers and subshells


The experiments described above measure the number of electrons with a certain principal quantum number, n, in other
words they are to be found in a certain shell. Within each shell of electrons there are, however, also subshells classified
by a second quantum number as s, p, d or f depending of their energy and shape. The subshells contain different
numbers of electrons.

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n=1 up to 2 electrons in an s subshell
n=2 up to 8 electrons in an s (2 e) and a p (6 e) subshell
n=3 up to 18 electrons in s (2 e), p (6 e) and d (10 e) subshells
n=4 up to 32 electrons in s (2 e), p (6 e), d (10 e) and f (14 e) subshells

To complicate matters, each subshell is made up of orbitals (e.g. a p sub-shell has three separate orbitals of equivalent
energy, each holding a maximum of 2 electrons), which are defined as regions in which there is the greatest probability
of finding a particular electron. Quantum mechanics (we’ll leave this to the Physicists!), has been used to determine that
all s orbitals are spherical, while p orbitals are roughly dumb-bell shaped (see below). All 3 p-orbitals are identical with
the exception of their axes of symmetry i.e. they are orientated at mutual right angles.

Shape and orientation


of p-orbitals

Representing the energy and electrons in boxes notation


Each orbital surrounding a nucleus is often symbolised by a box and the electrons that occupy the orbitals as arrows.
The orbital closest to the nucleus is associated with the electron shell which has a principal quantum number one and is
an s orbital and so is rather logically called a 1s orbital!! This can contain up to two electrons. Next up is the second
electron shell (n = 2), where the lowest energy sub-shell again consists of a single s orbital (2s). Once this is filled then
the p-subshell comes into play. The electrons occupy the three separate p orbitals singly at first (because of repulsion
effects), but start to pair up as the 4th electron is added.

The next orbital


Has n = 2

Once full we start


Filling a p sub-shell

Notice as you fill sub orbitals that you try not to pair up the spins of electrons if at all possible (see as you go from
boron (B) to fluorine (F). After this the second principal orbital is full and we go on to the third.

Filling electronic subshells


The orbitals always exist even if they are not occupied with electrons. How do we decide the order of filling the
electrons. The Electrons are filled in the sun-shells according to the scheme below. Each box represents an orbital.
Electrons are added successively to orbitals further and further from the nucleus up to the number given by the atomic
number with the minimum of paired spins (up and down electron arrows) in any orbital box.

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Order of sub-shell filling

1s 2s 2p 3s 3p 4s 3d
Examples
Write out electronic structure both in boxes and s,p,d,f notation for the elements magnesium Mg, silicon Si and
chlorine Cl. How do these compare to the electronic structures for Be, C and F above?
................................................................................................................................................................................................
................................................................................................................................................................................................
............................................................................................................................................. ...................................................
...........................................................................
What about transition elements and beyond: Try V (Z = 23), Cu (Z = 29), Br (Z = 35)
………………………………………………………………………………………………………………………………
………………………………………………………………………………………………………………………………
………………………………………………………………………………………………………………………………
Where is this all going??
What this exercise has shown (I hope) that electrons in atom ca only exist at certain energy levels (electron shells)
described by the principal quantum number. Each shell consists of sub-shells denoted by s, p, d or f, and the electrons
occupy the lowest available energy sub-level. These sub-shells are made up of orbitals, which are regions within an
atoms where there is the greatest probability of finding an electron. S-sub shells consists of only one orbital, while the p
sub-levels are made up of 3 orbital of equal energy. Orbitals can hold a maximum of 2 electrons. When sub-level is half
filled the addition of further electrons causes them to “pair-up”.
The total number of electrons is given by the atomic number from the periodic table. It is the outer most electrons in
the shell of the lowest energy (easiest to remove) that are responsible for bonding properties and chemical properties of
the elements. The outer electrons in elements from the same Periodic Group occupy similar sub shells (ie group 1 is
always ns1, group 7 (halogens) is always ns2,np5). This gives rise to the similar properties we see within the Periodic
Groups.
Patterns in atomic radius and ionisation energy (IE)
If we look at the first ionisation energy of the atoms down any group then it drops. This indicates that the electrons are
less firmly held in moving down a group. This is because the atoms are much larger and so the electrons are further
from the nucleus and are also more shielded from attractive force of the positively charged nucleus

If we look at the first ionisation energy along a period of elements then there is a general increase suggesting that the
electrons are more strongly held. This is indeed the case since electrons are added to the same shell there is no extra
shielding but extra attraction from the more positive nucleus. This also is reflected in smaller atomic size along a
Period of elements.

Note how the patterns are repeated


from period to period.

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Trends in atomic radius 1st and second short periods (magnified

If we look a bit more closely at the first short period Li – Ne (confusingly labelled period 2 above!), although the
general trend is an increase in IE, the values appear to fall into 3 distinct groups of 2, 3 and 3. The fall in IE when
moving from Be (1s2, 2s2) to B (1s2 2s2 2p1) comes about through extra shielding of additional electron by a full 2s sub-
shell. The extra electrons added to the p-sub shell when moving from B through to N are the same distance away from
then nucleus, while at the same time extra protons are being added to the nucleus. Because there is no change in
shielding the overall effect is that the extra positive nuclear charge exerts a greater attraction on the outer electrons and
IE increases. There is a slight hiccough however, when moving from N (1s2 2s2 2p3) to O (1s2 2s2 2p4). For the
reasoning set out previously (ie no change in electron distance and shielding coupled with the addition of an additional
proton in the nucleus), you would have expected the IE to increase. The fact that a decrease is observed is down to the
fact that a half filled p shell (i.e. 3 unpaired electrons in the p orbitals) is a favoured configuration. Notice that the same
2,3,3 grouping also crops up in the Na – Ar period. The highest IE across the period is observed for the inert gases (He,
Ar , Ne) confirming that the most energetically stable and favoured electronic configuration of all consists of fully
occupied s and p sub-shells (i.e ns2 np6)

Oxidation and reduction; what is it and why?


We have fleetingly encountered the terms oxidation and reduction earlier in the notes. In an engineering context, these
terms are core to the following processes: to extract iron from its ore we reduce it using carbon monoxide and when it
rusts then it is oxidised by oxygen gas. These two processes are opposite to one another and they refer to chemical
changes in which electrons are transferred from one species to another. They are perhaps the single most important
type of chemical reaction being responsible for burning, breathing, extraction and corrosion amongst other things.

Oxidation; a material which is oxidised loses electrons. In corrosion Fe = Fe 2+ + 2e

Reduction; a material that is reduced gains electrons. In iron extraction; Fe 3+ + 3e = Fe


Remember the saying OIL RIG; oxidation is loss and reduction is gain of electrons!!

A material that brings about the reduction of a species is a reducing agent and one that brings about the oxidation of a
material is an oxidising agent. During the reaction a reducing agent is oxidised and an oxidising agent is reduced.

Example during corrosion Iron is oxidised (Fe = Fe2+ + 2e) by the oxidising agent oxygen.
The oxygen is reduced (O2 + H2O + 4e = 4OH-). We will return to these later

Elements want full outer shells; the search for nobility


Ideally atoms want to be as stable as possible. The most stable elements are the noble gases with full outer electron
shells and all the other elements are in a permanent quest to obtain this most stable chemical structure. The elements

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can do this in a number of ways as we shall see through gaining or losing electrons (reduction or oxidation) or sharing
electrons with neighbouring atoms.
Metals have a low ionisation energy as we have seen so it is quite easy to remove electrons. In addition they generally
can gain a noble gas structure by losing a few electrons. For this reason metals often act as reducing agents in their
reactions loosing electrons and giving them away to other elements or compounds (for example in the corrosion of iron)

Non metals (eg oxygen) have 4 or more electrons in their outer shell and to lose all of these would be unfeasible due to
higher ionisation energies. Non metals tend to steal electrons from molecules they react with and act as oxidising
agents. An example would be oxygen in the corrosion of iron which ends up as oxide, O 2-, ions (eventually) having
gained two electrons.

In the following table we have considered the elements of the second period in the periodic table; The patterns will
obviously be similar for other periods since the electronic structures are so similar.

Examples
Li 1s2 2s1 lose 1 electron or gain 7 loses one to form Li+ strong RA

Be 1s2 2s2 lose 2 electrons or gain 6 loses 2 to form Be2+ RA

B 1s2 2s2 2p1 lose 3 electrons or gain 5 loses 3 to form B3+ or shares weak RA

C 1s2 2s2 2p2 lose or gain 4 electrons? tends to share! neither

N 1s2 2s2 2p3 lose 5 or gain 3 electrons shares or gains 3 to form N3- weak OA

O 1s2 2s2 2p4 lose 6 or gain 2 electrons gains 2 to form oxide O2- OA
S
F 1s2 2s2 2p5 lose 7 or gain 1 electrons gains 1 to form fluoride F- trong OA

Ne 1s2 2s2 2p6 no reactions!!


(NB: OA = oxidising agent, RA = Reducing agent)

DIY examples; predict whether the following are likely to act as reducing agents or oxidising agents in their reactions.
Chlorine (Cl), Potassium (K), Magnesium (Mg), Germanium (Ge)
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Foundation Chemistry (lectures 4-6): Holding materials together - chemical bonding
1. Bonding in elements
Bonding in metals
Metals have low ionisation energies as we have seen and the primary bonding in metals utilises this fact. The bonding
can be best visualised by imagining that the outer most electrons in the metal are ionised from the metal and become
delocalised in the structure. In this Giant Metallic structure the electrons act like a glue holding the positive metal ions
together. These delocalised electrons are free to move throughout the metal structure and are responsible for the fact
that metals conduct electricity. This is a vital function of metals as we have seen with major uses of copper and
aluminium in the power industries relying on this fact.

One of the key physical characteristics of metals is there ability to bend (deform plastically) to form shapes. This is due
to the movement of plains of atoms over one another. Metallic bonding is responsible for this phenomenon aswell in
that if the bonds between atoms were specific and the electrons were locked between the atoms then this ability would
be lost. Malleability and ductility are properties which rely on the fact that the electron glue in metals is still wet and
the layers of atoms can slide over one another.

Changing metallic properties


From group to group there are changes in the metallic properties. Consider the changes between sodium, magnesium
and aluminium from groups 1 to 3 in the third period respectively.
Density; increases due to larger atomic mass and smaller atoms
Physical strength; increase due to increasing numbers of outer electrons to act as glue
Electrical and thermal conductivity; increases due to increasing numbers of outer electrons
Ionisation energy; increases since atoms are smaller and electrons are more tightly bound

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Pure metals and alloys
Alloy materials are made to have enhanced properties over the pure metals that make them up. We have met a number
of examples of these from the early bronzes (copper and tin), to steels (iron, carbon and other metals eg chromium) and
modern light alloys (aluminium with elements such as copper and magnesium). Alloys can be of two basic types
Interstitial Alloys; Carbon steels; bonding is not metallic but carbon
atoms are physically stuck in the interstices. Carbon can be removed by
beating into wrought iron and also by the BOS process. The interstitial
carbon atoms physically lock the slip plains together preventing the
layers sliding over one another and improving the hardness and lowering
the malleability.

If too much carbon is retained in a steel then the structure becomes weak with the carbon atoms introducing lines of
weakness. This is why pig iron is such a poor material before is treated in the BOS process to lower the carbon levels.

Substitutional alloys; Brasses, bronzes, aluminium aircraft alloys and stainless steels.
The alloy atoms are bound into a giant metallic structure with all the outer electrons from all of the metal atoms
contributing to the electron glue holding the structure together. In these structures the slip plains are disrupted since the
alloying atoms are of differing sizes to the base metal atoms. This again makes the structure more rigid. Since the alloy
atoms are part of the chemical structure they cannot be beaten out as carbon can from steel.

Bonding in metalloids
Metalloids have a giant molecular structure. Here each atom in the structure
is connected to another by strong covalent bonds in which electrons are
shared. This gives a very rigid structure indeed. Since the electrons are
localised in the bonds between atoms the materials are not conductors of
electricity. Some electrons can jump from bond to bond under the influence
of potential and this gives rise to semiconduction. This is a very important
phenomenon which is responsible for most modern electronic equipment

Bonding in non-metals
The ionisation energy for non metals is much higher than for the metals in the same period. In order for the elements to
gain full outer shells of electrons they cannot loose electrons (since there are too many to lose) and they cannot remove
electrons from their identical neighbours. Instead the share electrons in what are known as covalent bonds. The
elements bind together in molecules with the bonds between atoms being very strong but bonding between molecules
much weaker. This intermolecular bonding is known as van der waals attraction and the weak bonding (a sort of
electronic gravitational attraction) means that most non metal elements are liquids poor solids or gases. The Van der
Waals attraction comes about due to transient dipoles between molecules due to the continually shifting electron density
in the atoms. (more later)

Properties of the non-metals;


These are not electrically conducting since there are no charge carriers available; the electrons are firmly held in the
shared covalent bonds.
They are often liquids gases or low melting point solids since they have very weak intermolecular forces
They often act as oxidising agents since their atoms only have full outer shells by sharing and in order to obtain
individual full outer shells they must steal electrons from a material (in other words oxidise it).

Summary of Bonding in Elements


Pure elements form structures by bonding individual atoms in various ways:
 Metals do so by metallic bonding and form giant metallic structures,

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 Metalloids use covalent bonding in which electrons are shared between atoms forming giant molecular
structures
 Non metals form discrete molecules in which atoms are strongly bound to one another using covalent bonds
with shared electrons but the molecules themselves are held together by weak secondary bonds (Van der Waals
bonding).

Bonding in Materials made up of Different Elements

Most of the Materials that we might use for Engineering applications are not of course pure elements but are rather
compounds of elements in different combinations. Most metals are found as alloys for example and there are many
metal/non metal and non-metals-non metals combinations that make up diverse ranges of materials from polymers, to
glasses, cements and salts. What are the forces that are holding these materials together

1. Giant Metallic Structures


We have already discussed that the compounds of metals and other metals have metallic bonding. In other words the
metal atom outer electrons are shared throughout the structure; this is known as delocalisation of electron density. This
gives rise to the properties of metals and their alloys. (see notes from last lecture).
Properties of metals related to their structure
1. High melting point due to strong metallic bonding
2. Usually solids at room temperature
3. Hard and yet malleable
4. Good Conductors of heat and electricity
5. Insoluble in both polar and non polar solvents

2. Ionic bonding and Giant Ionic Structures; Bonding compounds of metals and non metals
We saw last time that metals are often reducing agents and tend to give up electrons in their reactions forming positive
ions and non metals are oxidising agents and tend to gain electrons during their reactions forming negative ions.
Look at the table below. Previously we saw how elements want to attain the same favoured electronic configuration as
inert gases where the outer shell of electrons contain eight electrons (ns 2 np6). The first few elements in the period lose
their electrons to form positively charged ions (e.g. Na+, Mg2+), while elements at the end of the period gain electrons to
form negatively charged ions (S2- and Cl-).

Element Na Mg Al Si P S Cl Ar

Electronic 2,8,1 2,8,2 2,8,3 2,8,4 2,8,5 2,8,6 2,8,7 2,8,8


structure
No of outer 1 2 3 4 5 6 7 8
electrons
Ion formed Na+ Mg2+ Al3+ - - S2- Cl- Ar

Electronic 2, 8 2, 8 2, 8 2,8,8 2,8,8 2,8,8


structure of
ion

When metals and non metal react then they usual do so by electron transfer with the electrons going from the metal
which forms a positive ion to the non metal which forms a negative ion. They do so in order to achieve the lowest
energy and most stable electronic configurations similar to the next higher or lower noble gases in the periodic table.
Therefore sodium ions have an equivalent electronic structure to neon (next lowest inert gas), while chloride ions have
the same electronic configuration as argon (next highest).

A simple way of visualising the transfer of electrons is by the use of dots and crosses to represent the outer electrons
associated with each element, for example

Na + Cl  [Na]+ Cl
Don’t think that the electrons associated with Na are any different to those of Cl, they are identical. The dots and
crosses are used so that we can follow their transfer more easily. Try some others, what about the reaction of Mg (3s2)
with fluorine (2s2 2p5)?
………………………………………………………………………………………………………………………………
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This type of process, involving the complete transfer of electrons from one element to another, gives rise to a type of
bonding called IONIC (or electrovalent) in the substances formed.

Examples
sodium chloride aluminium oxide (alumina)
2Na + Cl2  2NaCl 4 Al + 3O2  2Al2O3
2(Na  Na+ + e) oxidation 4(Al  Al3+ + 3e)
Cl2 + 2e  2Cl- reduction 3(O2 + 4e  2O2-)

It is the electrostatic attraction between the oppositely charged ions that


holds the entire structure together. This is known as ionic bonding. X-ray
analysis of the crystal structures has shown that the ions are arranged in a
highly regular fashion in an ionic structure. For example sodium chloride
(common salt) has a simple cubic structure. Here each sodium ion is
surrounded by 6 chloride ions and vice versa in a giant structure that can
contain millions of ion. The cubic structure of salt crystals is clearly
visible when you sprinkle some onto your chips!

Representation of sodium chloride


structure

Ionic bonding is present in materials such as alumina, cement, rust and other salts. The magnitude of the opposite
charges is important in that bond strength increases with increasing charge difference. This makes alumina (Al 2O3) a
much harder material that sodium chloride (NaCl)

General Properties of ionic Compounds


(i) Ionic compounds have high melting points; the bonding is very strong and the crystal structures are very stable so
in order to melt the ionic structure large heat input is required. This results in very high melting points (remember in
aluminium extraction where melting point of alumina was ca 1850C)

(ii) Ionic compounds are hard and brittle; The strong electrostatic forces that hold ions together lock the structure into a
very rigid format and the ions are very difficult to prize apart. Ionic materials do not have slip plains like metals do
since there is no wet electron glue.

When a force is applied to an ionic material then it will not yield in a ductile fashion. When it yields it does so
catastrophically. Consider the sodium chloride structure above. If sufficient force is applied to force a plane of ions to
move then a situation is rapidly reached at which ions of the same charge face one another. These repel one another and
the material cleaves. Thus these are not slip planes but cleavage (!) plains. This property renders ionic materials very
brittle. This is whey cements contain aggregates and re-enforcement.

Note again that with alumina (Al3+ and O2-) the charges are very strong and so the structure is really very robust.
Alumina can be used very successfully as an abrasive since it is so hard and so tough.

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(iii) Dissolving Ionic Compounds; Ionic compounds often dissolve in certain types of solvents. Consider adding salt to
a soup or dissolving copper sulphate in water! Water is a good solvent for ionic materials. In order for the material to
dissolve the ions must be separated to form separate positive and negative species in solution. Water is a highly polar
molecule with positively charged hydrogen atoms and an overall negatively charged oxygen atom. This charge
separation comes about from the difference in electronegativity (more later) of the two atoms. Oxygen with a strong
affinity for electrons pulls electron density out of the covalent bond towards it polarising the bond.

The positively charged ends of the water molecules are attracted to the negative chloride ions ad can solubilise them and
the positive ions are removed by the negative polarity end of the water molecule.

The ions have been solvated by the solvent and formed solute ions in a solution!
There are many other solvents that are polar in nature and some of these are listed below.

acetone ethanol methanol chloromethane

Ionic compounds will not dissolve in non polar solvents

hexane carbon tetrachloride benzene toluene

(iv) Electrical Conductivity; Ionic compounds will not generally have high conductivity until they are molten in which
case then they are excellent conductors due to ionic movement between the positive and negative electrodes; this is how
we can extract aluminium from alumina using electrolysis.
Some ionic compounds are ceramic materials and show semiconducting properties like the metalloids. Many of the
transition metal oxides have this property to a greater or lesser degree. An example of this is Titanium oxide which is a
bright white material that is used as a pigment in paint and an optical brightener in materials as diverse as toothpaste
and chicken roll. Its semiconducting properties can result in Paint fade and degradation since absorption of photon
energy is enough to promote electrons into the conduction band of the semiconductor structure. The positive hole left
behind is an extremely efficient oxidant which can degrade the organic components of a coating such as the polymers or
dyes.

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3. Covalent Bonding: Bonding in non metal/non metal compounds
Hydrocarbons and polymers for example are made up of the non metal carbon and non metal hydrogen together with
other non metals (e.g. oxygen, nitrogen). In these situations there is not enough oxidising power to completely remove
electrons and form ions and ionisation energies are typically not low enough to form metallic structure with delocalised
electrons. In these situations electrons are shared between atoms so that they can obtain full outer shells (i.e. noble gas
structures). This sharing of electrons is known as covalent bonding.

Examples: One of the simplest molecules with a covalent bond is the hydrogen molecule. In hydrogen atoms each atom
contains one electron in a 1s orbital (remember that s orbitals are spherical in shape and represent the space around the
nucleus where an electron has the greatest probability of being found). In the hydrogen molecule the s orbitals of the
separate atoms can be considered to overlap as shown below

H H

Each atom has a share of 2 electrons – which is equivalent to having the same stable electronic structure as Helium. The
region of orbital overlap has an increased electron density and it is the extra attraction that the both nuclei have for this
region that constitutes a covalent bond (i.e. this attraction holds the molecule together).
The same dot/cross system we used for ionic bonding can be used to represent covalent bonding - see the example for a
chlorine atom below, where the chlorine atoms each share a pair of electrons:

Cl + Cl Cl Cl

What about trying the same thing for oxygen (O2 - 2 pairs shared) or nitrogen molecules (N2 – 3 pairs shared)
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Representations for a more complicated molecule
such as methane are given here, H
where the 4 outer electrons of the carbon atom are H Methane
shared between 4 hydrogen atoms. The dot/cross
representation of covalent bonds can be simplified H C H
by just drawing single lines to depict the covalent H C H
bonds.
H H

Dative covalent bonding


A normal covalent bond involves the sharing of a pair of electrons between 2 atoms, with each atoms contributing one
electron to the bond. However, in some cases the one of the atoms can donate both electrons. This type of bonding
where one atom supplies 2 electrons is called dative covalent bonding.
e.g. in an ammonia molecule, the N atom shares 3 of its outer electrons with three H atoms, with a pair remaining
unshared and not involved in bonding. However in an ammonium ion (NH 4+) which is formed for example when
ammonia gas reacts with hydrochloric acid (a white cloud of ammonium chloride is observed), a dative covalent bond is
formed between the unshared electron pair of the N atom and the H + ion. The ammonium ion carries a charge of +1,
which originates from the H+ ion.

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dative covalent bond
+
H

H N H + H+ H N H

H H
Usual covalent bonds
Predicting the shapes of covalent molecules
A simple fundamental principle can be used to predict the shape of covalently bonded molecule.
 Electron pairs repel each other and so try to get as far away from each other as possible
As a result there are a few fundamental molecule shapes which are commonly encountered and these depend on the
number of electron pairs in the outer shells of the atoms concerned.
e.g. BeCl2 (2 pairs), BCl3 (3 pairs) and methane (4 pairs) – see table below

180
109
120

What about molecules which consist of double or triple bonds? In terms of our simple theory of mutual repulsion of
electron pairs, double or triple bonds can easily be dealt with by adding the following rider: Multiple bonds are to be
treated as single bonds (i.e they can be considered as being 1 electron pair even though they may contain 2 or 3 shared
electron pairs). Examples: CO2 – linear, SO3 – trigonal planar.

In the above cases, each molecule consists of identical electron pairs. What about molecules where the electron pairs are
not identical, e.g. consider ammonia which has a pair of electrons which are unshared (known as a lone pair). Since
lone pairs are held closer to the central atom (N in the case of ammonia), we can add an another rider to our
fundamental principle for predicting molecule shapes which is that lone pairs exert a greater repulsion than bonding
pairs. The basic arrangement of electron pairs around the central N atom in ammonia will be tetrahedral. However, the
extra repulsion of the lone pair compresses the H-N-H bond angle to 107. For a water molecule, which has 4 electron
pairs (2 bonding and 2 lone pairs), again the basic arrangement of electron pairs is tetrahedral but the extra repulsion of
2 lone pairs reduces the H-O-H bond angle to 104.

Since lone pairs are held closer to the central atom (N


in the case of ammonia), we can add an another rider
to our fundamental principle for predicting molecule
shapes which is that lone pairs exert a greater
repulsion than bonding pairs. The basic arrangement
of electron pairs around the central N atom in
ammonia will be tetrahedral. However, the extra
repulsion of the lone pair compresses the H-N-H bond
angle to 107. For a water molecule, which has 4
electron pairs (2 bonding and 2 lone pairs), again the
basic arrangement of electron pairs is tetrahedral but
the extra repulsion of 2 lone pairs reduces the H-O-H

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bond angle to 104.

Intermolecular forces in covalent compounds


Covalent bonding occurs in all of the non metal non metal compounds such as carbon monoxide, carbon dioxide, iodine
(I2) and so on. Whilst the covalent primary bonding within molecules is very strong indeed, intermolecular bonds
(between molecules) are very weak forces. They arise either through the existence of permanent or induced
(temporary) dipoles which generate intermolecular attraction (e.g secondary bonding mechanisms such as Van der
Waals forces).

Permanent dipoles can exist due to the connection of highly electronegative atoms to less electronegative atoms. (e.g.
carbon to a chlorine in vinyl chloride for instance). Electronegativity is a measure of the attraction that atoms have for
bonding electrons within molecules (i.e. elements which want to acquire electrons in their chemical interactions are
called electronegative). It is a relative scale and as such as no units. Values for electronegativity for some of the most
common elements are given below:

H C N O F
2.1 2.5 3.0 3.5 4.0
P S Cl
2.1 2.5 3.0
Br (I)
2.8 (2.5)

Notice that electronegativity increases across are period and decreases down a group (see halogens). As a result of the
difference in electronegativity between constituent atoms, many covalently bonded molecules have ionic character, i.e.
they become polarised.

N.B. The  symbol means “slightly”


Therefore + means that the relevant
atom is slightly positively charged.

There is a specific form of intermolecular bonding via permanent dipole-permanent dipole interactions which is known
as hydrogen bonding. This is encountered in molecules which contain hydrogen attached to the most electronegative
elements (oxygen , fluorine, chlorine) As a result of the great difference in electronegativity, the bonds between H and
these atoms become permanently polarised with the H positively charged (i.e short of electrons). This results in the
negative end of 1 molecule being attracted to the positive end of another and so on.

A consequence of H bonding is that compounds


such as HF, NH3 and in particular water (see
right) have much higher boiling points than
would be expected for molecules of their size.

Induced dipole-dipole interactions


Dipoles can also be transiently generated in non polar molecules as a result of fluctuations in electron density around
molecules. Since the electrons in a molecule are in continual motion, at any given time the electron charge cloud around
the molecule may not be symmetrical (i.e. one side of the molecule may have more negative charge than the other – a
temporary dipole).
See below, where a symmetrical molecule is represented by a lozenge shape – at times t1 and t2, the distribution of
electron density is different. If the positive end of the molecule is pointing towards a neighbouring molecule (as in the
2nd row below), it can induce a negative charge on the closest part of its neighbour – creating an induced dipole.

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Induced dipoles will firstly acts one way and then another as a result of continuous electron movement - .ie. the dipoles
and hence the attractive forces between molecules continually form and then disappear. These weak, short range
intermolecular forces are known as Van-der-Waals forces and are significantly weaker than ionic and covalent bonds.
Evidence of the existence of Van-der-Waals forces has been obtained from studies on the behaviour of gases. In an
ideal gas, molecules should occupy negligible volume and not exert any forces on another. The ideal gas should then
obey the ideal gas equation where: PV = nRT, where P is pressure, V volume, R gas constant , T temperature and n =
number of moles (more about this later). However, real gases deviate from ideal behaviour, especially at high pressures.
The plot below represents ideal behaviour and actual behaviour of N 2 as pressure is increased. The quantity of PV/RT
for 1 mole of gas should remain constant (at PV/RT =1), but is reality shows a significant increase in value as pressure
is increased. The deviation occurs because as gas molecules are forced closer together, weak intermolecular forces
come into play.

Examples of Van-Der-Waals forces


The increase in boiling point for halogen molecules down group 7 (i.e. F2 < Cl 2< Br2, I2) results from stronger Van-der-
Waals forces with increasing molecular mass. Although Van-der-Waals forces in simple molecules such as methane are
small, total forces between large molecules (e.g. polymers) with many contact points can be very large. For example,
the physical strength of non-polar polymers such as poly(ethene) (or polyethylene) is dependent on a significant number
of interactions along the length of parallel polymer molecules.
The properties of graphite – an allotrope of carbon, is
heavily influenced by Van-der-Waals forces. Layers of
covalently bonded and hexagonally arranged carbon atoms
are held together only by Van-der-Waals forces. These are
strong enough to hold the layers together, bot not to stop
them easily sliding over one another.
Graphite is therefore soft (you can write with it!) and is a
well known solid lubricant.

N.B. Carbon has 3 allotropes (defined as different forms of the same element), diamond, graphite and C60 buckminster
fullerene – characterised for the first time back in the 1980’s and formed when graphite condenses after vapourisation
using high energy lasers.

Properties of non metal non metal (covalent) compounds


(i) melting points; The intermolecular bond forces control the melting points and since these are generally small then
the materials have low melting points and boiling points. As a result many of these compounds are often are gases and
liquids. Those materials that are solids generally have low melting points. If there is a high degree of molecular
polarity and if molecules are very large (as in the case of many polymers) then the materials can have higher melting
points.
(ii) Hardness and Malleability; Non metal non metal compounds are often liquids and gases and generally if they do
form solids these are soft and not rigid. The exception is with polymers however where massive molecular chains
intertwine (often assisted by permanent dipole interactions and chemical cross links) preventing molecules from easily
being separated in which case then materials can have reasonable physical properties.

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(iii) Conductivity; There are no electrical charge carriers in the compounds of non metals since electrons are localised
in the strong covalent bonds. Thus these compounds do not conduct electricity or heat. This is a very important fact
since the materials can be used as electrical insulators for wires and thermal insulators for heated apparatus.

(iv) Solubility; Simple molecular species will generally be soluble in solvents which have a simple molecular structure.
Highly polar solvents will not dissolve simple molecular species (there are of course exceptions such as sugar in a cup
of tea but in this case the sugar molecule has lots of polar OH groups which can interact via hydrogen bonds with the
water solvent.

This property is exceedingly important since it allows us to make versatile coatings such as paints and also to recycle
polymeric materials, as well as making solutions of materials.

4. Giant Molecular Materials; metalloid and non-metal compounds

The metalloid elements tend to form giant molecular compounds.


Silicon, silicon carbide (SiC) and diamond (C) all have the same
structure with atoms arranged in a tetrahedral arrangement with
each atom bound to four neighbours in strong covalent bonds with
shared electrons. The bond strength is enormous and this makes
the structures very strong. They are frequently used as cutting
equipment and in abrasives as a result of these properties which
are dependent of their very string bonding.

The structure of sand is also very similar with oxygen atoms acting as bridges between the silicon atoms. Note also that
the non metal carbon exists in a similar structure in its diamond allotrope. The graphite and buckminster fullerene
allotropes are also giant molecular structures but both have very different structures (see earlier).

Properties of Giant Molecular Structures


(i) melting point; Generally massive due to exceptionally stable structures with very strong bonding
(ii) Hardness and malleability; very hard indeed but not at all malleable. If enough force is supplied bonds will
permanently break and the material will shatter
(iii) Conductivity; some insulating and some semiconducting
(iv) These materials are insoluble in all solvents; this means that glass can be made into bottles for containing a wide
variety of liquids.

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