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.
iron 34.6%
1
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.
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
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.
2
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!!
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.
3
All an alchemist needs is an H bomb and a small Australian atoll!!!
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
4
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.
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.
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Calculate Ar for Mg if its isotope composition is as follows 24Mg (78.6%), 25Mg (10.1%), 26Mg (11.3%).
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5
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.
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 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!
6
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 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.
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.
7
Electronic Structure and Bonding; Holding Materials Together
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
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.
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
8
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
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!
9
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.
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.
10
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.
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.
11
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?
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What about transition elements and beyond: Try V (Z = 23), Cu (Z = 29), Br (Z = 35)
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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.
12
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)
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
13
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
B 1s2 2s2 2p1 lose 3 electrons or gain 5 loses 3 to form B3+ or shares weak RA
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
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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14
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.
15
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)
16
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).
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
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
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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17
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-)
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)
(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.
(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
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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
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109
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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.
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bond angle to 104.
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.
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.
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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.
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.
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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.
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).
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