Inorganic Chemistry is the study of the structures, properties, and behaviours incl.

reactions, of
elements, mixtures e.g. in solutions, and chemical compounds that do not contain carbon-hydrogen
bonds (such compounds are defined as "organic" for the purposes of chemical classification so study
of those compounds is considered organic chemistry).

Inorganic Chemistry Topics identifiable from the Periodic Table include, the chemistry of the
following elements, from left-to-right across the Periodic Table:

Groups I and II (of the Periodic Table), which are also known as the s-block elements.

The elements of Group I are known as Alkali Metals, and include: Lithium (Li), Sodium (Na),
Potassium (K), Rubidium (Rb), Caesium (Cs), and the rare radioactive element Francium (Fr).

The elements of Group II are known as Alkaline Earth Metals, and include: Beryllium (Be),
Magnesium (Mg), Calcium (Ca), Strontium (Sr), Barium (Ba), and the rare radioactive element
Radium (Ra).

Transition Metals, which are also known as the d-block elements.

Group III

This includes the non-metallic element Boron (B), Aluminium (Al), together with Gallium (Ga),
Indium (In) and Thallium (Tl).

Group IV

This includes the relatively common elements: Carbon (C), Silicon (Si), Germanium (Ge), Tin (Sn) and
Lead (Pb).

Note that the element carbon is one of the most important elements in organic chemistry but also
forms some compounds classified within inorganic chemistry, e.g. carbon monoxide (CO) and carbon
dioxide (CO2).

Group V

This includes: Nitrogen (N), Phosphorous (P), Arsenic (As), Antimony (Sb) and Bismuth (Bi).

Group VI

This includes: Oxygen (O), Sulphur (S), Selenium (Se), Tellurium (Te) and the radioactive element
Polonium (Po).

Group VII, which are known as the halogens.

This includes Fluorine (F), Chlorine (Cl), Bromine (Br), Iodine (I) and the radioactive element Astatine
(At).

Group 0, which are known as the Noble Gases and, due to their inactivity, also as "inert gases".

This includes Helium (He), Neon (Ne), Argon (Ar), Krypton (Kr), Xenon (Xe) and Radon (Rn).

Although the above indicates categories of elements, inorganic chemistry is not only about those
elements - but also about how they react and the compounds they form. Inorganic chemistry is a

1
huge subject area that includes all chemical reactions and compounds that are not or do not involve
organic compounds (i.e. substances which have carbon-hydrogen bonds).

Alternatively, it may be easier to answer the question what is inorganic chemistry by defining what it
is not:

That is - define chemistry as "the science of matter" then say that inorganic chemistry concerns the
chemical properties (as opposed to the physical chemistry) of non-organic chemical substances.
Then you would, of course, have to say that the chemical properties, incl. reactions etc. of organic
chemicals (which all contain carbon-hydrogen bonds) fall into the category of organic chemistry.

Basic (General) Types of Inorganic Chemistry Reactions

These include:

Combination Reactions (two or more substances combine to form a single chemical substance)

Decomposition Reactions (the opposite of "combination reactions", i.e. a substances decomposes

into its chemical parts)

Single Displacement Reactions (an atom or ion that forms part of a single compound is replaced by
an atom or ion of a different element)

Double Displacement Reactions (elements from two different compounds displace each other to
form compounds not present at the start of the reaction and which are due to different
combinations of the elements present in the original compounds)

Chemistry of Inorganic Compounds,

e.g. Chemistry of Salts

Salts are ionic compounds, some of which can form large crystal structures composed of cations
(positively charged ions) and anions (negative ions). There are many different salts. Common simple
examples include sodium chloride (NaCl), potassium chloride (KCl), calcium carbonate (CaCO3) and
sodium bicarbonate (NaHCO3).

ATOMIC AND PHYSICAL PROPERTIES OF THE PERIOD 3 ELEMENTS

describes and explains the trends in atomic and physical properties of the Period 3 elements from
sodium to argon. It covers ionisation energy, atomic radius, electronegativity, electrical conductivity,
melting point and boiling point.

ELECTRONIC STRUCTURE:

Na [Ne] 3s1

Mg [Ne] 3s2

Al [Ne] 3s2 3px1

2
Si [Ne] 3s2 3px1 3py1

P [Ne] 3s2 3px1 3py1 3pz1

S [Ne] 3s2 3px2 3py1 3pz1

Cl [Ne] 3s2 3px2 3py2 3pz1

Ar [Ne] 3s2 3px2 3py2 3pz2

ATOMIC AND PHYSICAL PROPERTIES OF THE PERIOD 3 ELEMENTS

This page describes and explains the trends in atomic and physical properties of the Period 3
elements from sodium to argon. It covers ionisation energy, atomic radius, electronegativity,
electrical conductivity, melting point and boiling point.

These topics are covered in various places elsewhere on the site and this page simply brings
everything together - with links to the original pages if you need more information about particular
points.

Atomic Properties

Electronic structures

In Period 3 of the Periodic Table, the 3s and 3p orbitals are filling with electrons. Just as a reminder,
the shortened versions of the electronic structures for the eight elements are:

Na [Ne] 3s1

Mg [Ne] 3s2

Al [Ne] 3s2 3px1

Si [Ne] 3s2 3px1 3py1

P [Ne] 3s2 3px1 3py1 3pz1

S [Ne] 3s2 3px2 3py1 3pz1

Cl [Ne] 3s2 3px2 3py2 3pz1

Ar [Ne] 3s2 3px2 3py2 3pz2

In each case, [Ne] represents the complete electronic structure of a neon atom.
First ionisation energy
The first ionisation energy is the energy required to remove the most loosely held electron from one
mole of gaseous atoms to produce 1 mole of gaseous ions each with a charge of 1+

It is the energy needed to carry out this change per mole of X.

The pattern of first ionisation energies across Period 3(ionisation energy is related to reactivity)

3
Notice that the general trend is upwards, but this is broken by falls between magnesium and
aluminium, and between phosphorus and sulphur.
Explaining the pattern
First ionisation energy is governed by:

 the charge on the nucleus;

 the distance of the outer electron from the nucleus;
 the amount of screening by inner electrons;
 whether the electron is alone in an orbital or one of a pair.

ACROSS PERIOD IONISATION ENERGY INCREASES DUE TO INCREASE IN NUCLEAR CHARGE.

DROP AT AL AS 3P NOT 3S (ENERGY LEVEL)
DROP AT SULPHUR DUE TO SPIN-PAIR REPULSION THEORY
ATOMIC RADIUS:

The figures used to construct this diagram are based on:

 metallic radii for Na, Mg and Al;

 covalent radii for Si, P, S and Cl;
 the van der Waals radius for Ar because it doesn't form any
strong bonds.

It is fair to compare metallic and covalent radii because they are both
being measured in tightly bonded circumstances. It isn't fair to
compare these with a van der Waals radius, though.

The general trend towards smaller atoms across the period is NOT
broken at argon. You aren't comparing like with like. The only safe
thing to do is to ignore argon in the discussion which follows.
Explaining the trend

4
 A metallic or covalent radius is going to be a measure of the
distance from the nucleus to the bonding pair of electrons.

From sodium to chlorine, the bonding electrons are all in the 3-level,
being screened by the electrons in the first and second levels. The
increasing number of protons in the nucleus as you go across the
period pulls the bonding electrons more tightly to it. The amount of
screening is constant for all of these elements.

Note: You might possibly wonder why you don't get extra screening from the 3s electrons in
the cases of the elements from aluminium to chlorine where the bonding involves the p
electrons. n each of these cases, before bonding happens, the existing s and p orbitals are
reorganised (hybridised) into new orbitals of equal energy. When these atoms are bonded,
there aren't any 3s electrons as such.

Electronegativity

Electronegativity is a measure of the tendency of an atom to attract a bonding pair of

electrons.

The Pauling scale is the most commonly used. Fluorine (the most electronegative element)
is assigned a value of 4.0, and values range down to caesium and francium which are the
least electronegative at 0.7.

The trend

The trend across Period 3 looks like this:

Notice that argon isn't included. Electronegativity is about the tendency of an atom to attract
a bonding pair of electrons. Since argon doesn't form covalent bonds, you obviously can't
assign it an electronegativity.

Explaining the trend

The trend is explained in exactly the same way as the trend in atomic radii.

As you go across the period, the bonding electrons are always in the same level - the 3-
level. They are always being screened by the same inner electrons.

All that differs is the number of protons in the nucleus. As you go from sodium to chlorine,
the number of protons steadily increases and so attracts the bonding pair more closely.

5
Electrical conductivity

 Sodium, magnesium and aluminium are all good conductors of electricity.

Conductivity increases as you go from sodium to magnesium to aluminium.
 Silicon is a semiconductor.
 None of the rest conduct electricity.

The three metals, of course, conduct electricity because the delocalised electrons (the
"sea of electrons") are free to move throughout the solid or the liquid metal.

In the silicon case, explaining how semiconductors conduct electricity is beyond the
scope of A level chemistry courses. With a diamond structure, you mightn't expect it to
conduct electricity, but it does!

The rest don't conduct electricity because they are simple molecular substances. There
are no electrons free to move around.

Melting and boiling points

The chart shows how the melting and boiling points of the elements change as you go
across the period. The figures are plotted in kelvin rather than °C to avoid having
negative values.

It is best to think of these changes in terms of the types of structure that we have talked
about further up the page.

The metallic structures

Melting and boiling points rise across the three metals because of the increasing strength
of the metallic bonds.

The number of electrons which each atom can contribute to the delocalised "sea of
electrons" increases. The atoms also get smaller and have more protons as you go from
sodium to magnesium to aluminium.

6
The attractions and therefore the melting and boiling points increase because:

 The nuclei of the atoms are getting more positively charged.

 The "sea" is getting more negatively charged.
 The "sea" is getting progressively nearer to the nuclei and so more strongly
attracted.

Note: Boiling point is a better guide to the strength of the metallic bonds than melting
point. Metallic bonds still exist in the liquid metals and aren't completely broken until
the metal boils.

I don't know why there is such a small increase in melting point as you go from
magnesium to aluminium. The boiling point of aluminium is much higher than
magnesium's - as you would expect.

Silicon

Silicon has high melting and boiling points because it is a giant covalent structure. You
have to break strong covalent bonds before it will melt or boil.

Because you are talking about a different type of bond, it isn't profitable to try to directly
compare silicon's melting and boiling points with aluminium's.

The four molecular elements

Phosphorus, sulphur, chlorine and argon are simple molecular substances with only van
der Waals attractions between the molecules. Their melting or boiling points will be lower
than those of the first four members of the period which have giant structures.

The sizes of the melting and boiling points are governed entirely by the sizes of the
molecules. Remember the structures of the molecules:

Phosphorus

7
Phosphorus contains P4 molecules. To melt phosphorus you don't have to break any
covalent bonds - just the much weaker van der Waals forces between the molecules.

Sulphur

Sulphur consists of S8 rings of atoms. The molecules are bigger than phosphorus
molecules, and so the van der Waals attractions will be stronger, leading to a higher
melting and boiling point.

Chlorine

Chlorine, Cl2, is a much smaller molecule with comparatively weak van der Waals
attractions, and so chlorine will have a lower melting and boiling point than sulphur or
phosphorus.

Argon

Argon molecules are just single argon atoms, Ar. The scope for van der Waals attractions
between these is very limited and so the melting and boiling points of argon are lower
again.

e)_defines ceramic as;

Rigid material that consists of an infinite three-dimensional network of sintered crystalline

grains comprising metals bonded to carbon, nitrogen or oxygen.

Note:

The term ceramic generally applies to any class of inorganic, non-metallic product
subjected to high temperature during manufacture or use.

In the first sentence, the word "sintered" refers to the process of sintering. Sintering
happens when you heat a powdered material to a temperature below its melting point,
and new bonds are formed between the grains of powder to form one large mass.

The most commonly used definition (including by CIE) tends to include what the note
says. There are several modern ceramic materials which don't actually involve a metal.
The syllabus, for example, includes

silicon(IV) oxide,

aluminium oxide

magnesium oxide

and there is a past question which tells you that silicon carbide, SiC, is used in ceramics,
and asks you to deduce things about it.

Chemguide: Support for CIE A level Chemistry

8
 Learning outcomes 4(f) and 4(g)

These statements are a brief introduction to ceramic materials.

Before you go on, you should find and read the statements in your
copy of the syllabus.

The IUPAC Gold Book defines ceramic as

Rigid material that consists of an infinite three-dimensional

network of sintered crystalline grains comprising metals
bonded to carbon, nitrogen or oxygen.

Note:
The term ceramic generally applies to any class of
inorganic, non-metallic product subjected to high
temperature during manufacture or use.

In the first sentence, the word "sintered" refers to the process

ofsintering. Sintering happens when you heat a powdered
material to a temperature below its melting point, and new bonds
are formed between the grains of powder to form one large mass.

The most commonly used definition (including by CIE) tends to

include what the note says. There are several modern ceramic
materials which don't actually involve a metal. The syllabus, for
example, includes silicon(IV) oxide, and there is a past question
which tells you that silicon carbide, SiC, is used in ceramics, and
asks you to deduce things about it.

This is such a huge topic that I will just stick closely to what the
syllabus asks.

Statement 4(f)

This deals with the properties of some ceramic materials, and talks
about the physical properties of ceramics in terms of their
structures.

The structures

9
I have a problem with this, because I disagree with the syllabus
statement! This says ". . . in terms of their giant molecular
structure". A giant molecular structure (I prefer the term giant
covalent structure) consists of covalent bonds holding together
huge numbers of atoms. If you have been working through
previous statements in Section 4, you will already have read about
these in learning outcome 4(e)(iii).

The problem is that some of the ceramics mentioned in 4(g) aren't

covalent. Magnesium oxide is ionic, and aluminium oxide is also
mainly ionic. They do indeed have giant structures, but they have
giant ionic structures.

Other more complex ceramics will contain both ionic and covalent
bonds, some of which may be highly polar.

What is, however, true is that ceramics all have giant structures of
one type or another, with strong bonds between the atoms (or ions)
which make them up.

The physical properties

Strength

The strong bonds holding the atoms (or ions) together in three
dimensions will make the ceramic hard and strong, but also brittle.

Think about a ceramic wall or floor tile as a simple example. The

tile is obviously hard, and you can stand on a floor tile, or place
heavy furniture on it without it breaking - so it is strong. On the
other hand, it isn't difficult to break a tile in half by snapping it,
especially if you score a shallow line on it first with a cutting tool - it
is brittle.

This is unlike a metal, which would bend before it fractured - you

can bend or stretch metals. Atoms in metals can roll over each
other without breaking the bonds. In a ceramic, you either have to
break covalent bonds in three dimensions or, if you distort an ionic
lattice, it brings like charges together, which splits the lattice apart.
The lattice is either all in one piece, or else broken apart.

Melting points

Ceramics have high melting points because of the need to break

the strong covalent or ionic bonds holding the giant structure
together. It takes a very high temperature to do this.

10
Electrical conductivity

Most ceramics are good electrical insulators. If they are covalent,

there are no free electrons to move around. If they are ionic, the
ions aren't free to move in the solid.

Examples of electrically conducting (including superconducting)

ceramics are beyond the scope of this syllabus.

Statement 4(g)

This deals with the uses of modern ceramic materials involving

magnesium oxide, aluminium oxide and silicon(IV) oxide, and the
relationship with their structures.

Magnesium oxide

Ceramics made from magnesium oxide are used in (amongst other

things):

 furnace linings (refractory bricks), because the ceramic has

a high melting point (strong forces in the giant structure);
 heating elements (for example for electric cookers),
because the ceramic is good electrical insulator (no free
electrons, and the ions aren't free to move in the solid).

A heating element will often have a metal core which heats

up when an electric current flows through it. For obvious
safety reasons, this has to have an electrically insulating
layer around it with a high melting point (typical ceramic
properties), and a further metal layer on the outside to
protect the brittle ceramic.

Aluminium oxide

Various web sources describe this as the most important oxide

ceramic.

Uses of aluminium oxide ceramics include:

 high temperature and high voltage electrical insulators,

because the ceramic has a high melting point and is a good

11
 electrical insulator (strong attractions in the giant structure;
no free electrons, and the ions aren't free to move either);
 replacement hip joints. Hip joints are a ball and socket
arrangement, and the ball or socket can both be made of
aluminium oxide ceramic material. The strong forces holding
the aluminium and oxide ions together make it very resistant
to wear. Aluminium oxide is also chemically resistant
because of the large amount of energy needed to separate
the ions.

The photograph (taken from Wikipedia) shows an artificial

hip joint in pieces. This one has a ceramic ball, but a
polythene cup.
Silicon(IV) oxide (silicon dioxide)

Uses of silicon dioxide ceramics include:

 as furnace linings (refractory bricks) in furnaces for the production of

glass, because the giant covalent structure has a very high melting point
due to the strength of the Si-O covalent bonds in three dimensions;
 to make ceramic tiles to protect the space shuttle. The tiles are light, and
have a high melting point.

You will notice that I haven't specifically quoted two of the uses suggested in the
syllabus - the use in glass and crockery. The reason is that although silicon(IV)
oxide, for example, is used to make glass, the resulting glass isn't pure silicon(IV)
oxide.

Instead, it will be a complex lattice with (mainly) ionic bonds to various other
metal ions present.

This diagram (also taken from Wikipedia) shows a possible structure for a
particular glass.

12
 To describe this as silicon(IV) oxide would be chemical nonsense!

It is possible to make a ceramic containing pure silicon(IV) oxide which looks like
glass, but it isn't normal glass. The only times I ever came across it were in a
chemistry lab.

The problem with pottery is even worse. Various kinds of pottery are made by
heating to high temperatures various clays or mixtures of clay with other things.
The results are chemically very complex. It would be completely misleading to
describe pottery as being made of any of the ceramic materials mentioned in this
syllabus statement.

Note: Up to the November 2012 papers, all you needed to do was to identify "baked clay found
in crockery" as containing a giant structure. You just had to recognise baked clay as a ceramic,
and know that ceramics had giant structures. You didn't need to know what that structure was.

P3 Reactions with water

Na

13
Mg
Cold water:

S l aq g
Hot water/steam: ( Mg is s)

Al
S l s g
Si
(s) (l) (s) (g)
P These have no reaction with water.

S These have no reaction with water.

Cl
G l aq aq
In sunlight

Ar There is no reaction between argon and water.

Sodium has a very exothermic reaction with cold water producing hydrogen and a colourless solution of sodium
hydroxide.sodium lump darts around the surfaces andd fizzes

Magnesium has a very slight reaction with cold water, but burns in steam.

A very clean coil of magnesium dropped into cold water eventually gets covered in small bubbles of hydrogen which float it to the
surface. Magnesium hydroxide is formed as a very thin layer on the magnesium and this tends to stop the reaction.

Magnesium burns in steam with its typical white flame to produce white magnesium oxide and hydrogen.

Note: If you are heating the magnesium in a glass tube, the magnesium also reacts with the glass. That leaves dark grey products
(including silicon and perhaps boron from the glass) as well as the white magnesium oxide.

Notice also that the oxide is produced on heating in steam. Hydroxides are only ever produced using liquid water.

P3 REACTIONS WITH OXYGEN

Na

Mg

Al

Si

P PHOSPHORUS(III)OXIDE (take 4P INSTEAD OF P₄)

PHOSPHORUS(IV) OXIDE

S
2SO₂+O₂ ―――――> 2SO₃
Cl Despite having several oxides DOESNOT REACT DIRECTLY WITH OXYGEN
Ar NO REACTION WITH ARGON

14
Oxide+water

Sodium

Sodium burns in oxygen with an orange flame to produce a white solid mixture of sodium
oxide

Magnesium

Magnesium burns in oxygen with an intense white flame to give white solid magnesium
oxide.

Note: If magnesium is burns in air rather than in pure oxygen, it also reacts with the
nitrogen in the air. You get a mixture of magnesium oxide and magnesium nitride formed.

Aluminium
Aluminium will burn in oxygen if it is powdered, otherwise the strong oxide layer on the
aluminium tends to inhibit the reaction. If you sprinkle aluminium powder into a Bunsen
flame, you get white sparkles. White aluminium oxide is formed.
Silicon
Silicon will burn in oxygen if heated strongly enough. Silicon dioxide is produced.

15
Note: There is disagreement between various web or textbook sources about the
temperature needed to ignite the silicon, varying from 400°C to well over 1000°C. In fact,
there isn't a "right" answer to this. It depends on what sort of silicon you are talking about
and how finely divided it is. For example, one of the amorphous (non-crystalline powder)
forms of silicon even catches fire spontaneously in air at room temperature. Other forms
need higher temperatures and a richer oxygen supply.
Phosphorus
White phosphorus catches fire spontaneously in air, burning with a white flame and
producing clouds of white smoke - a mixture of phosphorus(III) oxide and phosphorus(V)
oxide.
The proportions of these depend on the amount of oxygen available. In an excess of
oxygen, the product will be almost entirely phosphorus(V) oxide.
Note: You may come across these oxides written as P2O3 and P2O5. Don't use these
forms! They are as logical as writing, say, ethene as CH2 and ethane as CH3.
Sulphur
Sulphur burns in air or oxygen on gentle heating with a pale blue flame. It produces
colourless sulphur dioxide gas.
Extra notes (physcical properties of p3 oxides)

Are molecular oxides and aluminum oxide is amphoteric (with ionic bonding with some
covalent character)

16
,,

Learning outcome 9.2(b)

state and explain the variation in oxidation number of the oxides (sodium
to sulfur only) and chlorides (sodium to phosphorus only) in terms of
their valence shell electrons

This statement - 9.1(f) - deals with the oxidation numbers (oxidation states)
of the elements in Period 3 in their oxides and chlorides. 9.1(j) is involved in
the explanation for this.

Before you go on, you should find and read the statements in your copy of
the syllabus.

Oxidation state (oxidation number)

The terms "oxidation number" and "oxidation state" are used

interchangeably.

I tend use the term "oxidation state", and you will find that used on the page
I will point you to in a moment. But for the rest of this page, I will stick to
"oxidation number", because that is what the CIE syllabus uses.

It may well be that this is the first time you have come across the term
oxidation number. In fact, it first comes up in Section 6 of the syllabus, but
that section contains some quite difficult material, and it is quite likely that
you won't have done it before coming to this work on the Periodic Table.

17
So the first thing you have to do is to get comfortable with the idea of
oxidation number.

You will find this on the page about oxidation states (oxidation numbers).

Don't try to rush this - spend an hour or so on it if necessary. You won't

make sense of the rest of this part of the syllabus unless you understand
how to use oxidation numbers.

Variation of the oxidation numbers in the chlorides

Just as in the earlier statement 9.1(e), we are only concerned with the
chlorides of the elements from sodium to phosphorus.

In each case, the chlorine in the compound is the more electronegative

element, and so the chlorine always has a negative oxidation number - in
each case, -1.

Before you read on, work out the oxidation number of the other element in
each of the following compounds.

NaCl, MgCl2, Al2Cl6, SiCl4, and PCl5

Don't waste time trying to learn these oxidation numbers - just quickly work
them out if you need them. It is important that you can do this. I will discuss
a CIE question further down the page where you would get completely
confused if you tried to learn this rather than understand it.

Let's look at the most complicated-looking one - Al2Cl6. You can then apply
exactly the same principles to the other simpler ones.

All of these are electrically neutral compounds, and so the sum of all the
oxidation numbers is zero. If the oxidation number of the aluminium is "x",
and the chlorine is -1, then:

2x + 6(-1) = 0

2x = +6

x = +3

So the oxidation number of the aluminium is +3.

You would then go through the same simple process for the other
chlorides, and find the following oxidation numbers:

18
 Na +1

Mg +2

Al +3

Si +4

P +5

In each case the oxidation number is the same as the number of electrons
in the outer energy level of the atom in question - what the syllabus
describes as "their valance shell electrons".

These compounds all involve the element using all of its outer electrons in
the bonding - either giving them away to form positive ions, or sharing them
to form covalent bonds. In each of these cases, there is a movement of
electrons away from the element towards the more electronegative
chlorine. That is why all of these oxidation numbers are positive.

Although it isn't specifically mentioned by the syllabus, it is worth exploring

the phosphorus case a little bit further, because phosphorus forms two
chlorides, PCl3 and PCl5.

You will find the bonding in these discussed towards the bottom the page
on covalent bonding.

The oxidation number of the phosphorus in PCl3 is +3. Work it out!

The point I am trying to make is that the maximum possible oxidation

number of an element in Period 3 is going to be the same as the number of
electrons in its outer energy level, but that smaller oxidation numbers are
also possible where not all of the outer electrons are used.

You will see another example of this in the oxides of sulphur (discussed
below).

Variation of the oxidation numbers in the oxides

19
In this case, we are concerned with the oxides of the elements from sodium
to sulphur.

The oxygen in the compound is always the more electronegative element,

and so always has a negative oxidation number - in each case, its usual -2.

So work out the oxidation numbers of the other element in each of the
following:

Na2O, MgO, Al2O3, SiO2, P4O10, SO2 and SO3.

Don't just read this next bit - work them out!

Na in Na2O +1

Mg in MgO +2

Al in Al2O3 +3

Si in SiO2 +4

P in P4O10 +5

S in SO3 +6

S in SO2 +4

You can see that the pattern is much the same as before. The maximum
oxidation state shown by the elements in this period is the same as the
number of outer electrons.

in the case of sulphur, the maximum oxidation state is +6. All of sulphur's 6
outer electrons are being used to make the bonds in sulphur trioxide. But
that doesn't have to be the case.

In sulphur dioxide (where sulphur has an oxidation state of +4), only 4 of its
outer electrons are involved in bonding.

You might wonder why sulphur wasn't included amongst the list of
chlorides in the previous section. I suspect it is because it would break the
tidy pattern. In compounds between sulphur and chlorine, the highest
oxidation state shown by the sulphur is +4, not +6. In other words, you can
have SCl4, but not SCl6.

20
There is, however, a compound SF6. So sulphur only shows its maximum
oxidation state when it is combined with oxygen or fluorine. The reason for
this isn't all that difficult, but isn't required by the syllabus.

A look at what CIE actually ask in exams

You must expect exam questions to go beyond what is actually asked in

the syllabus. Examiners can justify this provided you could work the answer
out from things which are on the syllabus.

I am going to explore an example to show you the sort of problems that

arise. It comes from November 2009 Paper 22.

As a part of the question, they gave a list of chlorides of the elements from
sodium to sulphur and asked you to give the oxidation numbers of the
elements, and then explain the variation across the period.

Here is the list of compounds, and I have worked out the oxidation numbers
for you:

NaCl +1

MgCl2 +2

AlCl3 +3

SiCl4 +4

PCl3 +3

SCl2 +2

Notice several things:

 They have given a different formula for aluminium chloride from the
one in the syllabus.
 The list contains a sulphur chloride, despite the fact that the syllabus
specifically excludes chlorides of sulphur. The syllabus says:
"Variation in oxidation number . . . of the chlorides (sodium to
phosphorus only)".

21
  The phosphorus chloride in the question isn't the same one as listed
in the syllabus in statement 9.1(e). I know that the list isn't repeated
in 9.1(f), but the implication is strongly that it is the same list.
 This is the most important thing. The last two chlorides in the
question (phosphorus and sulphur) don't have the element in its
highest possible oxidation state - unlike those in the syllabus.

This means that if you had simply learnt that the maximum oxidation
number shown by the elements from sodium to phosphorus was the same
as the number of outer electrons, you couldn't have done this question.

And if you can't work out the correct oxidation numbers, you obviously can't
explain the variation across the period.

You must be able to understand what you are doing.

I have a real problem with the answers to the other part of this question
asking you to explain the variation across the period!

The Examiner's Report says about part (a)(ii):

A significant number of candidates struggled with this part

which is specifically mentioned in sections 9.1(f) and (j), of the
Syllabus.

For Na to Al, Examiners were expecting candidates to describe

the loss of electrons to give the noble gas configuration of Ne.
For Si to S, on the other hand, they expected candidates to
describe the sharing of electrons to give the noble gas
configuration of Ar.

. . . and I take issue with that!

There is no mention in the syllabus of explaining this in terms of noble gas

structures. In fact, for the chlorides actually mentioned in the syllabus
you can't explain this in terms of noble gas structures, because the chloride
of phosphorus and the oxides of phosphorus and sulphur quoted in the
syllabus don't involve noble gas structures in the phosphorus or sulphur.

In this instance, it also isn't necessarily true that the aluminium in AlCl3 has
a neon structure. That is only true if the AlCl3 is ionic. But in the vapour at a
high enough temperature, AlCl3 is a simple molecule, covalently bound -
and the aluminium has 6 electrons in its outer level. Even in solid AlCl3, the
bonding is ionic with a high degree of covalent character.

22
What the positive sign in the oxidation numbers actually shows is some
loss of electrons in each case, either their full removal to make ions, or their
movement towards the chlorine in a polar covalent bond.

What the size of the oxidation numbers (+1, +2, +3, +4) shows is the
number of electrons actually involved in this process.

c) describe the reactions of the oxides with water

23
uptill now:

CHLORIDES:
1.reactions with chlorine (to give NaCl , MgCl 2, Al2Cl6, SiCl4, PCl5)
2. e) describe and explain the reactions of the chlorides with water
3.chemical bonding in chlorides

 At room temperature, solid aluminum chloride has an ionic lattice with significant of covalent character.
 At temperatures around 180 - 190°C (depending on the pressure), aluminum chloride coverts to
its molecular form, Al2Cl6. This causes it to melt or vaporize due to comparatively weak intermolecular
attractions.
 As the temperature increases further, more AlCl3 molecules are formed.
Solid aluminum chloride does not conduct electricity at room temperature because the ions are not free to move.
Molten aluminum chloride (only possible at increased pressures) is also nonconductive, because it has lost its ionic
character.

Aluminum chloride reacts dramatically with water. A drop of water placed onto solid aluminum chloride produces
steamy clouds of hydrogen chloride gas. Solid aluminum chloride in an excess of water still splutters, but instead
an acidic solution is formed. A solution of aluminum chloride of ordinary concentrations (around 1 mol dm -3, for
example) has a pH around 2-3. More concentrated solutions have a lower pH.

P3 Reaction with chlorine for descr.:

http://www.chemguide.co.uk/inorganic/period3/elementsreact
Na

Mg

Al
Alcl3 volatile solid and AL2CL6 vapour phase)
Si
(l) volatile PRODUCT
P PCL3 pale colourless liquid

PCL5 pale yellow solid

24
 S

Cl It obviously doesn't make sense to talk about chlorine reacting with itself, and argon doesn't
Ar react with chlorine.
Reaction of chlorides with water:explaination
Emphasise that NaCl and MgCl2 merely dissolve (to form pH 7 solutions containing dissociated ions)
whereas the rest undergo hydrolysis. With a small amount of water AlCl3 gives Al2O3 + HCl, but
with an excess a solution containing [Al(H2O)5(OH)]2+ + H++ Cl- ions is formed.
http://www.chemguide.co.uk/inorganic/period3/chlorides.html#top

25
d) describe and explain the acid/base behaviour of oxides and hydroxides
including, where relevant, amphoteric behaviour in reaction with acids
and bases (sodium hydroxide only)
http://www.chemguide.co.uk/inorganic/period3/oxidesh2o.html
GO THROUGH SCHEME WORK:

chrome-
extension://cbnaodkpfinfiipjblikofhlhlcickei/pdfviewer/web/viewer.html?file=http://stud
yguide.pk/Past%20Papers/CIE/International%20A%20And%20AS%20Level/9701%20-
%20Chemistry/9701_nos_sw_9.pdf

GRROUP2:

Learning outcome 9.2(a)

This statement wants you to be able to describe the reactions between the Group 2
elements and oxygen, water and dilute acids.

Before you go on, you should find and read the statements in your copy of the
syllabus.

Reactions with oxygen

You will find these discussed on the page reactions of the group 2 elements with air
or oxygen.

That page includes more information than you need.

 First of all, notice that the syllabus talks about the reaction with oxygen
- not with air. That means that you can ignore any mentions of the reactions
with nitrogen.

26
  Secondly, notice that the syllabus, under "Content", only wants the reactions
of the elements from magnesium to barium. Beryllium isn't mentioned. It is
possible for the examiners to ask you to predict some properties of beryllium
(or of radium at the bottom of the group) in statement 9.2(d), but we will deal
with that problem on the page about 9.2(d) later.
 This syllabus statement just says "describe" - not "describe and explain". All
you need are simple descriptions and equations.
 The syllabus section on Periodicity (9.1) doesn't expect you to know about
the formation of peroxides. However, CIE have asked a multiple-choice
question about the structure of the peroxide ion in barium peroxide. For
safety, you should be aware of the formation of peroxides by strontium and
barium as described on the Chemguide page. You need to realise that the
peroxide ion carries a single negative charge on both oxygen atoms. You will
find a diagram of that in the Explanations section of that page.

Important update September 2014: CIE have been asking multi-choice questions (most recently in
June 2014 Paper 12 Q12 and Paper 13 Q19) about what colour flame Group 2 metals burn with. The
choices included (amongst others) green or white for barium, and red or white for strontium.

If you have read my Chemguide page about this, you will know that I describe both of these flames
as white with some coloured tinges. In other words both "white" and a colour are parts of the
description of the flame. I see these questions as being invalid, and impossible to answer for anyone
who has actually seen these metals burning rather than reading about them.

For CIE exam purposes, you must therefore choose the flame test colour for burning the metals
calcium (red), strontium (red) and barium (green). There is obviously no problem with magnesium
(white)!

Reactions with water

You will find these discussed on the page reactions of the group 2 elements with
water.

For this statement, all you need to know are the descriptions - particularly for
magnesium and calcium, which seem to be what are mainly asked in exams. The
reactions for strontium and barium will look similar to calcium, but with faster
reactions.

The explanations will come later in statement 9.2(d).

Reactions with dilute acids

27
You will find these discussed on the page reactions of the group 2 elements with
acids.

You can ignore the references to beryllium, especially with nitric acid. You can also
ignore references to anything other than dilute acids.

REACTIONS OF THE GROUP 2 ELEMENTS WITH

OXYGEN

The reactions with oxygen

Formation of simple oxides

On the whole, the metals burn in oxygen to form a simple metal oxide.

Beryllium is reluctant to burn unless it is in the form of dust or powder.

Beryllium has a very strong (but very thin) layer of beryllium oxide on its

28
surface, and this prevents any new oxygen getting at the underlying
beryllium to react with it.

"X" in the equation can represent any of the metals in the Group.

It is almost impossible to find any trend in the way the metals react with
oxygen. It would be quite untrue to say that they burn more vigorously as
you go down the Group.

What the metals look like when they burn is a bit problematical!

 Beryllium: I can't find a reference anywhere (text books or internet) to the

colour of the flame that beryllium burns with. My best guess would be the
same sort of silvery sparkles that magnesium or aluminium powder burn
with if they are scattered into a flame - but I don't know that for sure.
 Magnesium, of course, burns with a typical intense white flame.
 Calcium is quite reluctant to start burning, but then bursts dramatically into
flame, burning with an intense white flame with a tinge of red at the end.
 Strontium: I have only seen this burn on video. It is also reluctant to start
burning, but then burns with an intense almost white flame with red tinges
especially around the outside.
 Barium: I have also only seen this burn on video, and although the
accompanying description talked about a pale green flame, the flame
appeared to be white with some pale green tinges.

Update September 2014: In response to a question from a student, I tried to find the barium
video which I mention above, but couldn't. Instead, YouTube currently has three short video
clips showing barium metal burning. All of these show intense white flames with no convincing
trace of green.

29
Formation of peroxides

Strontium and barium will also react with oxygen to form strontium or
barium peroxide.

Strontium forms this if it is heated in oxygen under high pressures, but

barium forms barium peroxide just on normal heating in oxygen. Mixtures of
barium oxide and barium peroxide will be produced.

The strontium equation would look just the same.

The Explanations

Trying to pick out patterns in the way the metals burn

There are no simple patterns. It would be tempting to say that the reactions
get more vigorous as you go down the Group, but it isn't true.

The overall amount of heat evolved when one mole of oxide is produced
from the metal and oxygen shows no simple pattern:

30
If anything, there is a slight tendency for the amount of heat evolved to get
less as you go down the Group.

But how reactive a metal seems to be depends on how fast the reaction
happens - not the overall amount of heat evolved. The speed is controlled
by factors like the presence of surface coatings on the metal and the size of
the activation energy.

You could argue that the activation energy will fall as you go down the
Group and that will make the reaction go faster. The activation energy will
fall because the ionisation energies of the metals fall

In this case, though, the effect of the fall in the activation energy is masked by
other factors - for example, the presence of existing oxide layers on the metals,
and the impossibility of controlling precisely how much heat you are supplying to
the metal in order to get it to start burning.

Note: It is interesting to look at what happens if you heat a very reactive metal like potassium in
air. The potassium melts at a low temperature and almost instantly turns into a pool of molten
potassium oxide. The activation energy is so low that the reaction happens very quickly at quite
a low temperature. There is often no trace of flame. It can be fairly boring!

Magnesium, on the other hand, has to be heated to quite a high temperature before it will start
to react. The activation energy is much higher. There are also problems with surface coatings. It
is then so hot that it produces the typical intense white flame.

It would obviously be totally misleading to say that magnesium is more reactive than potassium
on the evidence of the bright flame. You haven't had to heat them by the same amount to get
the reactions happening.

31
Why do some metals form peroxides on heating in oxygen?

Beryllium, magnesium and calcium don't form peroxides when heated in oxygen,
but strontium and barium do. There is an increase in the tendency to form the
peroxide as you go down the Group.

The peroxide ion, O22- looks llike this:

The covalent bond between the two oxygen atoms is relatively weak.

Now imagine bringing a small 2+ ion close to the peroxide ion. Electrons in the
peroxide ion will be strongly attracted towards the positive ion. This is then well
on the way to forming a simple oxide ion if the right-hand oxygen atom (as drawn
below) breaks off.

We say that the positive ion polarises the negative ion. This works best if the
positive ion is small and highly charged - if it has a high charge density.

Note: A high charge density simply means that you have a lot of charge packed into a small
volume.

Ions of the metals at the top of the Group have such a high charge density
(because they are so small) that any peroxide ion near them falls to pieces to give
an oxide and oxygen. As you go down the Group and the positive ions get bigger,
they don't have so much effect on the peroxide ion.

Barium peroxide can form because the barium ion is so large that it doesn't have
such a devastating effect on the peroxide ions as the metals further up the Group

32
REACTIONS OF THE GROUP 2 ELEMENTS WITH
WATER
Beryllium

Beryllium reacts with steam at high temperatures (typically around 700°C or

more) to give white beryllium oxide and hydrogen. (Equation just like the
magnesium one below.)

Magnesium

Magnesium burns in steam to produce white magnesium oxide and hydrogen

gas.

Very clean magnesium ribbon has a very slight reaction with cold water. After
several minutes, some bubbles of hydrogen form on its surface, and the coil of
magnesium ribbon usually floats to the surface. However, the reaction soon stops
because the magnesium hydroxide formed is almost insoluble in water and forms
a barrier on the magnesium preventing further reaction.

Note: As a general rule, if a metal reacts with cold water, you get the metal hydroxide. If it
reacts with steam, the metal oxide is formed. This is because the metal hydroxides thermally
decompose (split up on heating) to give the oxide and water.

Calcium, strontium and barium

These all react with cold water with increasing vigour to give the metal hydroxide
and hydrogen. Strontium and barium have reactivities similar to lithium in Group 1
of the Periodic Table.

Calcium, for example, reacts fairly vigorously with cold water in an exothermic
reaction. Bubbles of hydrogen gas are given off, and a white precipitate (of
calcium hydroxide) is formed, together with an alkaline solution (also of calcium
hydroxide - calcium hydroxide is slightly soluble).

33
 The equation for the reactions of any of these metals would be:

The hydroxides aren't very soluble, but they get more soluble as you go down the
Group. The calcium hydroxide formed shows up mainly as a white precipitate
(although some does dissolve). You get less precipitate as you go down the
Group because more of the hydroxide dissolves in the water.

Summary of the trend in reactivity

The Group 2 metals become more reactive towards water as you go down the
Group.

Explaining the trend in reactivity

Beryllium as a special case

There is an additional reason for the lack of reactivity of beryllium compared with
the rest of the Group. Beryllium has a strong resistant layer of oxide on its surface
which lowers its reactivity at ordinary temperatures. However, the oxide layer
breaks up above 750°C and exposes the beryllium metal surface below it, and so
the protection then fails.

Looking at the enthalpy changes for the reactions

If you calculate the enthalpy change for the possible reactions between
beryllium or magnesium and steam, you come up with these answers:

Notice that both possible reactions are strongly exothermic, giving out
almost identical amounts of heat. However, the magnesium reaction is
much faster. The explanation for the different reactivities must lie
somewhere else

When Group 2 metals react to form oxides or hydroxides, metal

ions are formed.

34
 Note: This is a simplification in the case of beryllium. Beryllium oxide isn't fully ionic. There isn't
enough electronegativity difference between the beryllium and oxygen for the beryllium to lose
control of the bonding pair of electrons and form ions. The approach we are taking here is in line
with the sort of answer that you would be expected to give at A level. Thinking about beryllium
as an entirely different case would make this argument unnecessarily complicated.

The formation of the ions from the original metal involves various stages all
of which require the input of energy - contributing to the activation energy of
the reaction. These stages involve the input of:

 the atomisation energy of the metal. This is the energy needed to

break the bonds holding the atoms together in the metallic lattice.
 the first + second ionisation energies. These are necessary to
convert the metal atoms into ions with a 2+ charge.

After this, there will be a number of steps which give out heat again -
leading to the formation of the products, and overall exothermic reactions.

The graph shows the effect of these important energy-absorbing stages as

you go down Group 2.

Notice that the ionisation energies dominate this - particularly the second
ionisation energies. Ionisation energies fall as you go down the Group.
Because it gets easier to form the ions, the reactions will happen more
quickly.

35
Summarising the reason for the increase in reactivity as you go down
the Group

The reactions become easier as the energy needed to form positive ions
falls. This is mainly due to a decrease in ionisation energy as you go down
the Group. This leads to lower activation energies, and therefore faster
reactions.

REACTIONS OF GROUP2 + DILUTE ACIDS:

G2 Dilute sulphuric acid
Be These are just like the reactions with dilute hydrochloric acid, and
you have probably been familiar with the reaction between
& magnesium and dilute sulphuric acid almost since you started
Mg doing chemistry. Bubbles of hydrogen are formed, together with
colourless solutions of beryllium or magnesium sulphate.

For example:

Calcium sulphate is sparingly soluble, and you can think of

strontium and barium sulphates as being insoluble. That means
that you will get a layer of insoluble sulphate on all of these which
will slow down the reaction or stop it entirely.

In the calcium case, you will get some hydrogen produced

together with a white precipitate of calcium sulphate.

G2 Dilute Nitric Acid(all metal react of grp2 react except Be as it

depends on its ttype of manufacture) refer
http://www.chemguide.co.uk/inorganic/group2/reactacids.html

Reactions with nitric acid

These are more complicated. When most metals react with most
acids, what they are actually doing is reducing hydrogen ions to
hydrogen gas by adding electrons to the hydrogen ions. The
metal is, of course, oxidised to positive metal ions because it
loses electrons.

36
 But nitrate ions are also easily reduced to products like nitrogen
monoxide and nitrogen dioxide.

So metals reacting with nitric acid tend to give oxides of nitrogen

rather than hydrogen. If the acid is relatively dilute, you tend to
get nitrogen monoxide, although this immediately reacts with
oxygen in the air to make brown nitrogen dioxide.

Concentrated nitric acid gives nitrogen dioxide

Mg These will produce hydrogen from nitric acid provided the acid is
very dilute, but even so, it will be contaminated with nitrogen
oxides. Colourless solutions of the metal nitrates will be formed.

Taking magnesium as an example, if the solution is very dilute:

At moderate concentrations (and even with very dilute acid, this

will happen to some extent):

And with concentrated acid:

Learning outcome 9.2(b)

This statement wants you to be able to describe the behaviour of the Group
2 oxides, hydroxides and carbonates with water and with dilute acids.

Before you go on, you should find and read the statements in your copy of
the syllabus.

The oxides

Reaction of the oxides with water

37
All of the oxides from magnesium oxide to barium oxide react with water, at
least to some extent, to form hydroxides.

Magnesium oxide

If you shake some white magnesium oxide powder with water, nothing
seems to happen - it doesn't look as if it reacts. However, if you test the pH
of the liquid, you find that it is somewhere around pH 9 - showing that it is
slightly alkaline.

There must have been some slight reaction with the water to produce
hydroxide ions in solution. Some magnesium hydroxide is formed in the
reaction, but this is almost insoluble - and so not many hydroxide ions
actually get into solution.

Calcium oxide

If you add water to calcium oxide ("quicklime"), there is a very exothermic

reaction to produce calcium hydroxide ("slaked lime"). The calcium oxide
swells up and a lot of steam is produced as the heat boils the water.

If you add enough water (or use a very small amount of calcium oxide), a
colourless solution of calcium hydroxide is formed with a pH around 12.
The solution is often called "lime water".

The pH isn't any higher because calcium hydroxide is only slightly soluble.
A saturated solution of calcium hydroxide is only about 0.015 mol dm-3 at
room temperature.

There is a quirky bit of video showing this reaction on YouTube.

Strontium and barium oxides

These will be similar to calcium oxide, except that the hydroxides are rather
more soluble, and so the pH of the solutions formed increase slightly - to
about 13.5 for barium hydroxide.

38
The equations are just like the magnesium oxide or calcium hydroxide
ones.

Reaction of the oxides with dilute acids

These are all basic oxides, reacting with acids to give a salt and water.

They will react with dilute hydrochloric to give colourless solutions of the
chloride, and with dilute nitric acid to give colourless solutions of the nitrate.

With dilute sulphuric acid, the situation is more confusing because calcium
sulphate is only sparingly soluble, and strontium or barium sulphates are
virtually insoluble. The precipitates formed will coat the oxides, and the
reactions will stop. It would be impossible to make, say, barium sulphate
like this - you couldn't separate the unreacted barium oxide from the barium
sulphate coating.

Sample equations:

The hydroxides

Reaction of the hydroxides with water

The hydroxides don't react with water. None of them are very soluble, but
the solubility increases as you go down the Group. See the beginning of
the page about the solubility of the hydroxides (etc).

Reaction of the hydroxides with dilute acids

The hydroxides behave in exactly the same way as the oxides.

Sample equations:

39
The carbonates

Reaction of the carbonates with water

The carbonates don't react with water. All of them are virtually insoluble in
water. You will find a bit more detail on the page about the solubility of the
hydroxides (etc).

Reaction of the carbonates with dilute acids

Carbonates react with acids to give a salt, carbon dioxide and water.

All of these carbonates will react with dilute hydrochloric acid or nitric acid
to give a colourless solution of the chloride or nitrate and carbon dioxide
gas.

For example:

But the same problems exist as before with sulphuric acid. If you add dilute
sulphuric acid to a marble chip (calcium carbonate), you will get a few
bubbles of carbon dioxide for a very short time, and then the reaction stops.
The marble chip becomes coated with insoluble calcium sulphate, so
stopping the reaction.

The only Group 2 carbonate to react properly with dilute sulphuric acid is
magnesium carbonate, because magnesium sulphate is soluble.

40
 








 Learning outcome 9.2(b)
 This statement wants you to be able to describe the behaviour of the
Group 2 oxides, hydroxides and carbonates with water and with
dilute acids.
 Before you go on, you should find and read the statements in your
copy of the syllabus.

 The oxides
 Reaction of the oxides with water
 All of the oxides from magnesium oxide to barium oxide react with
water, at least to some extent, to form hydroxides.

 Magnesium oxide
 If you shake some white magnesium oxide powder with water,
nothing seems to happen - it doesn't look as if it reacts. However, if
you test the pH of the liquid, you find that it is somewhere around pH
9 - showing that it is slightly alkaline.
 There must have been some slight reaction with the water to produce
hydroxide ions in solution. Some magnesium hydroxide is formed in
the reaction, but this is almost insoluble - and so not many hydroxide
ions actually get into solution.


 Calcium oxide
 If you add water to calcium oxide ("quicklime"), there is a very
exothermic reaction to produce calcium hydroxide ("slaked lime").
The calcium oxide swells up and a lot of steam is produced as the
heat boils the water.
 If you add enough water (or use a very small amount of calcium
oxide), a colourless solution of calcium hydroxide is formed with a pH
around 12. The solution is often called "lime water".

 The pH isn't any higher because calcium hydroxide is only slightly
soluble. A saturated solution of calcium hydroxide is only about 0.015
mol dm-3 at room temperature.

41
 There is a quirky bit of video showing this reaction on YouTube.

 Strontium and barium oxides
 These will be similar to calcium oxide, except that the hydroxides are
rather more soluble, and so the pH of the solutions formed increase
slightly - to about 13.5 for barium hydroxide.
 The equations are just like the magnesium oxide or calcium
hydroxide ones.

 Reaction of the oxides with dilute acids
 These are all basic oxides, reacting with acids to give a salt and
water.
 They will react with dilute hydrochloric to give colourless solutions of
the chloride, and with dilute nitric acid to give colourless solutions of
the nitrate.
 With dilute sulphuric acid, the situation is more confusing because
calcium sulphate is only sparingly soluble, and strontium or barium
sulphates are virtually insoluble. The precipitates formed will coat the
oxides, and the reactions will stop. It would be impossible to make,
say, barium sulphate like this - you couldn't separate the unreacted
barium oxide from the barium sulphate coating.
 Sample equations:




 The hydroxides
 Reaction of the hydroxides with water
 The hydroxides don't react with water. None of them are very soluble,
but the solubility increases as you go down the Group. See the
beginning of the page about the solubility of the hydroxides (etc).

 Reaction of the hydroxides with dilute acids
 The hydroxides behave in exactly the same way as the oxides.
 Sample equations:




 The carbonates
 Reaction of the carbonates with water

42
 The carbonates don't react with water. All of them are virtually
insoluble in water. You will find a bit more detail on the page about
the solubility of the hydroxides (etc).

 Reaction of the carbonates with dilute acids
 Carbonates react with acids to give a salt, carbon dioxide and water.
 All of these carbonates will react with dilute hydrochloric acid or nitric
acid to give a colourless solution of the chloride or nitrate and carbon
dioxide gas.
 For example:


 But the same problems exist as before with sulphuric acid. If you add
dilute sulphuric acid to a marble chip (calcium carbonate), you will get
a few bubbles of carbon dioxide for a very short time, and then the
reaction stops. The marble chip becomes coated with insoluble
calcium sulphate, so stopping the reaction.
 The only Group 2 carbonate to react properly with dilute sulphuric
acid is magnesium carbonate, because magnesium sulphate is
soluble.

 E)OBJECTIVE

43
SOLUBILITY OF THE HYDROXIDES, SULPHATES AND CARBONATES OF THE
GROUP 2 ELEMENTS IN WATER

Solubility of the hydroxides

 The hydroxides become more soluble as you go down the Group.

Solubility of the sulphates

 The sulphates become less soluble as you go down the Group.

Solubility of the carbonates

🔺 The carbonates tend to become less soluble as you go down the

Group.

d)describe the thermal decomposition of the nitrates and carbonates

44
45
46
 i

ii

47
 Learning outcomes 9.2(e) and 9.2(f)

These statements want you to know about some simple uses of magnesium and
calcium compounds.

Before you go on, you should find and read the statements in your copy of the
syllabus.

Magnesium oxide

Magnesium oxide is used to make linings for some furnaces. It is known as a

refractory material - which just means that it is resistant to heat. You may have
come across this on the CIE page about ceramics.

Magnesium oxide has a high melting point (2852°C) and so resists the high
temperatures in a furnace. Its melting point is high because of the strong ionic bonds
between the small Mg2+ and O2-ions.

Magnesium oxide is a basic oxide, and so can't be used in furnaces where acids
may be present. However, it doesn't react in any way with other basic materials
such as calcium oxide.

For that reason, it can be used in the furnaces involved in iron and steel making. In
the Blast Furnace, limestone is added as one of the raw materials. That

48
decomposes to form basic calcium oxide in the heat of the furnace. This would have
no effect on a refractory furnace lining like magnesium oxide which is itself basic.

In the basic oxygen steel making process, quicklime (calcium oxide) is added to the
furnace to remove impurities in the iron. Again, this won't affect the magnesium
oxide lining.

Note: Follow this link if you are interested in a bit more detail about iron and steel. This
is not required by the syllabus.

The use of lime in agriculture

This is quite confusing, because the word "lime" can mean three entirely different
things!

 Powdered limestone (calcium carbonate) is often called lime.

 On heating, calcium carbonate decomposes to make calcium oxide, which is
known as "quicklime", but is often just called lime.
 If you add water to calcium oxide, it reacts to form calcium hydroxide, which
is known as "slaked lime" or "hydrated lime", but is also often just called lime.

It isn't totally clear from the CIE syllabus or the past papers I had available at the
time of writing which of these CIE is looking for. I suspect that it is calcium oxide or
hydroxide, but I can't be sure.

To some extent that doesn't actually matter, because all three types of lime are used
for exactly the same purpose - to raise the pH of the soil.

Many crop plants grow best at a pH of around 6 - 6.5. However, over time, soils tend
to become more acidic than this. All of the various kinds of lime react with acids in
the soil, and therefore raise the pH. Calcium carbonate and oxide and hydroxide all
react with acids.

The use of lime and fertilisers together

A multiple choice question that I looked at asked about what would happen if a
farmer treated a field with lime together with a nitrogen fertiliser containing an
ammonium compound. If you knew about ammonium salts (which you will come
across later if you haven't already done so), you would know that they react with
bases to give off ammonia gas.

So you could work out what happens - but it is easier if you have met it before!

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If you added a strong base like calcium oxide or hydroxide at the same time as the
ammonium compound, then they would quickly react to release ammonia into the
atmosphere - wasting the fertiliser.

If you just stir together a solid mixture of calcium oxide or hydroxide and an
ammonium compound in the lab, you can smell (cautiously!) the ammonia being
released

Part 4. Fullerenes and carbon nanotubes

 What are fullerenes? What is the formula and

structure of Buckminsterfullerene? What are fullerenes used
for? What is a 'bucky ball'? What is a nanotube?
 Apart from the carbon allotropes of diamond and graphite, a 3rd
form of carbon exists as fullerenes or 'bucky balls'. [see table of
diagrams]
o There is also amorphous carbon e.g. soot or charcoal, but this
is mainly chemically modified impure graphite.
o Allotropes are different atomic, molecular arrangements of the
same element in the same physical state.
 They consist of hexagonal rings of carbon atoms (like in graphite or
graphene) and alternating pentagonal and heptagonal carbon rings to
allow curvature of the surface (see diagram further down) producing
molecules that have a complete hollow shape.
o They are a sort of a hollow 'cage' or 'ball' or 'closed tube'
shaped molecules of pure carbon atoms. [see table of
diagrams]
o The carbon atoms still form three bonds per carbon atom,
and most of their carbon atom rings are hexagonal, but some
are five and seven membered rings.
o Fullerenes are NOT nanoparticles BUT they are smaller
molecular versions equating to sections of the tiny molecular
carbon tubes called carbon nanotubes,
 AND they are very interesting molecules in themselves
and provide a way into studying carbon nanotubes in
terms of their molecular structure and applications in
nanotechnology.
 These fullerenes (and carbon nanotubes) are quite
different from other forms of carbon e.g. in the form of
soot, graphite or diamond.

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 The carbon-carbon bonds in Buckminster Fullerene
C60 (shown on right) form a pattern like a soccer ball and this
fullerene is a brownish-reddish-magenta colour when dissolved in
organic solvents. It is a black? solid insoluble in water.
o The first fullerene to be discovered (C60) was named
Buckminsterfullerene (fullerene-60), is derived from the
American architect R. Buckminster Fuller who invented the
geodesic dome design in building construction.
 Other typical fullerenes have formulae such as ...
o C28, C32, C50, C70 which is red in solution, rugby ball shape - US
American football shape
o In these fullerenes the carbon atoms lie at vertices of a
polyhedron with 12 pentagonal faces with a minimum of two
hexagonal faces. [see table of diagrams]
 They are NOT considered giant covalent structures and are
classed as relatively small simple molecules, even those above Cn!
o They do dissolve in organic solvents giving coloured solutions.
o The colour depends on the solvent ranging from red to deep
purple and violet.
o They are the only soluble allotrope of carbon.
o Although solid, their melting points are not that high.
 What are the uses of fullerenes?
o Fullerene molecules can be used for drug delivery into the
body, as lubricants, as catalysts and in the form of carbon
nanotubes can be used for reinforcing composite
materials, eg sports equipment like tennis rackets (see
further down the page).
o They have many chemical synthetic and pharmaceutical
applications.
 The may be use as vehicles to carry drugs into cells, the
cage like fullerene molecules could contain a drug, and
the combination can pass easily through the wall of a
target cell.
o Chemical derivatives of fullerenes have fascinating electrical
and magnetic behaviour including superconductivity and
ferromagnetism (nano nature?, beyond the scope of this
page?)
o C60 is an optical limiter.
 When light is shone on it, a solution of fullerene-60 turns
darker instantly and the more intense the light, the darker
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 it gets, so the intensity of transmitted light is limited to a
maximum value.
 This limiting light transmittance property can be used in
the design of safety goggles in intense light situations
e.g. people working with laser beams.
o Fullerenes may used in certain medical applications - an
example of nanomedicine
 The idea is to use the very small fullerene molecules to
easily deliver drugs directly into cells in a highly
controlled manner.
 This is possible because the extremely small
diameter of the nanoparticle fullerenes (which act
like a cage to hold the drug molecules) allows them
to readily pass through cell membranes and readily
absorbed into the body.
 Fullerene molecules have very a high surface area /
volume ratio and may be used in the development of new
types of catalysts in the chemical industry, perhaps
catalyst molecules can be attached to fullerene structure.
o Fullerenes are being developed that have excellent lubricating
properties (maybe superior to lubrication oils) and these
lubricants significantly reduce friction in moving metal parts of
machines from cog wheels to ball bearings and maybe artificial
joints after orthopaedic operations on hips and knees!
 Fullerenes are mentioned here to illustrate the different forms of
carbon AND they can be formed into continuous tubes to give very
strong fibres of 'pipe like' molecules called 'nanotubes'.
o These nanotube molecules-particles behave differently
compared to bulk carbon materials like graphite and the much
smaller fullerene molecules.
 What are Nanotubes? - What is the molecular structure of carbon
nanotubes? (sometimes called 'buckytubes') and of what use are
they in carbon nanotechnology?
o Carbon nanotubes are essentially long cylindrical
fullerenes.
o Carbon nanotubes are one of the most intensively studied and
characterised used nanomaterials, consisting of tiny cylinders
of made carbon atoms, no wider than a strand of DNA with a
wide range of properties of great use to materials scientists.
 You can think of them as stretched out fullerenes, but
using many more carbon atoms. [see table of diagrams]
 Despite being composed of so many carbon atoms, they
are still considered nanomaterials because their diameter
is of nanoscale proportions.

52
o In other words, lots of varieties of carbon nanotubes, differing
in size and atomic arrangement can have very different
properties.
 You can also fabricate multiple layered carbon
nanotubes like an elongated 'Russian doll'!
 These presumably would make a stronger
material?
o Uses of carbon nanotubes - long fullerene molecules, one
basis of the relatively new nanotechnology
o Carbon nanotubes have a very high tensile strength, very good
electrical conductivity and a relatively high thermal conductivity
- good conductors of electricity and heat.
 They are used as a component in strong composite
materials.
 This is partly due to carbon nanotubes have a high
length to diameter ratio and they don't easily break
when stretched.
o Some carbon nanotubes are excellent insulators,
semiconductors or conduct electricity as well as copper!
 Nanotubes can conduct electricity and will find
technological applications as electrical circuits in
computers and instruments (see last section on type A
and B carbon nanotubes).
 They can be used as semiconductors or 'miniature
wires' in electrical circuits and of great use in miniature
electronic circuitry in computers and other electronic
devices.
o They act as a component of industrial catalysts for certain
reactions whose economic efficiency is of great importance
(time = money in business!).
 The catalyst can be attached to the nanotubes which
have a huge surface are per mass of catalyst 'bed'.
 They large surface combined with the catalyst ensure
two rates of reaction factors work in harmony to increase
the speed of an industrial reaction so making the process
more efficient and more economic.
o Carbon nanotube fibres are very strong and so they are
used in 'composite materials' e.g. reinforcing graphite and
plastics with in carbon fibre tennis rackets, golf clubs.
 Nanotubes can be stronger than steel with only 1/6th the
weight, so adding strength without adding weight to
sports equipment.

53
  Bundles of the nanotubes, processed into fibres, have
very high tensile strength and can be much stronger than
steel on a weight for weight basis.
 Note that pure the carbon allotrope graphite is a soft
slippery solid with low physical strength.
o Carbon nanotubes could be used to make tiny mechanical
devices, molecular computers as well as extremely strong
materials.
o Carbon nanotubes are an important additive in other oil based
lubricants to enhance their performance.
 Additives are added to lubricating oils to improve their
effectiveness in reducing friction and as a chemical
stabiliser eg to inhibit thermal degradation of the oil in
high temperature situation, but I'm not sure what the
function of carbon nanotubes is in this case? I suspect
the reasons involve some complex physics of viscosity
well beyond the scope of these notes!
o The structure and properties of carbon nanotubes [see
table of diagrams]
 The main cylinder or tube is made only from carbon
hexagons (essentially graphite layers curved into a
'molecular pipe').
 However pentagons are needed to close the structure at
the ends or form spherical or rugby football shaped
molecules.
 The carbon nanotube molecule is held together by strong
covalent carbon-carbon bonds which extends all along
the nanotube or all round the smaller 'bucky ball'
molecules as they are sometimes called.
 Single or multiple-walled carbon nanotubes tubes, made
from concentric nanotubes (i.e. one tube inside a larger
nanotube), can be formed.
 Note that graphite is soft and malleable.
 The behaviour of electrons depends on the length of the
carbon nanotube, so some forms are excellent
conductors and others
are semiconductors.
 This is a typical nanoscale (quantum) effect,
 i.e. there are major differences between the
properties of the bulk material the size-dependent
properties on the nanoscale (silver is another good
example).

54
  Diagrams of the molecular structure of buckminster fullerenes
('fullerenes') and nanotubes (graphite shown for comparison, one
isolated layer is the same as graphene)

One of the A longer buckminsterfullerene

A section of multi-
simplest which is 'rugby ball' or 'sausage'
layered graphite
'buckyballs' C60 shaped, C72 etc.

A section of a carbon nanotube e.g. 6 x 100 nm, the ends would be like those
of the 'sausage' above right. All images © doc brown

 Some further discussion on

molecular structure
 One possible skeletal formula representation of a layer of graphite or
a molecule of graphene (graphene described in next section) is
shown above in Kekule style as in aromatic compounds.
o The C-C bond length in graphite or graphene is 0.142 nm,
midway between a single C-C carbon-carbon bond length of
0.154 nm and a double C=C carbon-carbon bond of 0.134 nm.
o The carbon-carbon bond order in graphite/graphene is 1.33,
which follows from 4 valency electrons overlapping from each
carbon atom BUT each carbon atom forms three C-C bonds.
 The bond order is 1.5 in benzene, the average of a
carbon-carbon single bond (bond order 1) and

55
 carbon=carbon double bond (bond order 2), but there is
a C-H bond too.
o The C-C-C bond angle is exactly 120o, what you would expect
for the planar carbon hexagons.
o In graphite the planar hexagonal ring layers of carbon atoms
are 0.335 nm apart.

 How you get the curvature in

the molecular shape of fullerenes and the ends of nanotubes. The C-
C-C bond angles for a planar carbon pentagon will be ~108o and for
a planar carbon hexagon ~120o.
 Note the analogous structure of carbon nanotubes and graphite
layers or the graphene molecule.
o Nanotubes are essentially a single layer of graphite (or a
molecule of graphene) wrapped around to form an elongated
tube-like molecule, they only consist of hexagonal rings
throughout the sides of the nanotubes.
 An example of the versatility of carbon nanotubes based on two
possible fabrications, giving subtle differences in molecular structure
and properties is described below.
o The two diagrams below illustrate a short section of long
carbon nanotubes displaying the two principal symmetries of
hexagonal carbon ring orientation with respect to the central
axis of a carbon nanotube.
 These two types of single walled nanotubes can be made
by folding graphenes/graphite sheets in different
directions (but at 90o with respect to each form).

56
 o etc.

and etc.
o In A the longest axis of the carbon hexagons is aligned at
90o to the principal axis of the carbon nanotube.
 A is sometimes referred to as the 'armchair' form and is
electrically semiconducting and can be used as a semi-
conductor transistor in microelectronic circuits.
o In B the longest axis of the carbon hexagons is aligned in the
same direction as the principal axis of the carbon nanotube.
 B is sometimes called the zig-zag form and has metal
like electrical conductivity and can be used in micro-
circuitry i.e. one of the tiniest possible electrical circuit
dimensions.

14.4 - Allotropes of carbon

14.4.1 Describe and explain the structures and properties of diamond, graphite and

fullerene. Students should recognize the type of hybridization present in each allotrope and

the delocalization of electrons in graphite and C60 fullerene.

Allotropy

Allotropes are different physical forms of the same element. All elements are made up
uniquely of their own atoms and therefore any physical differences must be a consequence
of how the atoms are joined together - their arrangement within the bulk structure.

57
 Many elements exhibit allotropy as there are often varous ways in which the atoms can be
linked together into molecules and also different ways in which the molecules can be
arranged to make larger structures.

In the case of carbon, the atoms form either giant macromolecular structures (diamond and
graphite) in which all of the atoms in the bulk structure are joined together by covalent
bonds making giant molecules, or smaller molecules (buckminster fullerene) in which there
are only discrete molecules made up of 60 carbons in a structure resembling a football
(hence the nickname 'bucky balls')

Diamond

Each carbon in a diamond crystal is bonded to four other carbon atoms making a giant
macromolecular array (lattice). As each carbon has four single bonds it is sp3 hybridised and
has tetrahedral bond angles of 109º 28'

Properties of diamond

 hardest substance known to man

 brittle (not malleable)
 insulator (non-conductor)
 insoluble in water

58
 very high melting point

Physical properties of diamond explained by considering the structure and bonding

Property Explanation Diamond structure

Many strong covalent bonds

Hard
holding the structure together

All of the bonds are directional

and stress will tend to break the
structure (In a malleable
substance, such as for example a
Brittle
metal, the bonding is non-
directional and can still act if the
particles are displaced with
Click on the
respect to one another).
image with the
left mouse
All of the valence (outer shell)
electrons are used in bonding. button and drag
The bonds are sigma and the to get a different
Insulator electrons are located between view.
the two carbon nuclei being
bonded together. None of the
electrons are free to move (if you can't see
the image you

There are only very weak Van have to

der Waal's attractions between download chime)
the carbon atoms and the water
Insoluble
molecules whereas the carbon
atoms are bodned very tightly to
one another.

Many strong covalent bonds

holding the structure together -
Very high melting point
it requires massive amounts of
energy to pull it apart

Graphite

Again the carbon atoms are bonded together to make a giant structure but in this case all
of the carbons are bonded to only three neighbour and are sp 2 hybridised. As the
sp2 hybridisation results in planar structures, there are giant 2 dimensional layers of carbon
atoms and each layer is only weakly linked to the next layer by Van der Waal's forces.

Physical properties of graphite explained by considering the structure and bonding

59
 Property Explanation Graphite structure

Many strong covalent bonds

holding the structure together
but only in 2 dimensions. The
Soft and slippery
layers are free to slide easily
over one another. Graphite
powder is used as a lubricant.

All of the bonds are directional

within a layer and stress across a
layer will tend to break them.
Brittle
Graphite rods used for
electrolysis easily break when
dropped.
Click on the
image with the
Only three of the valence (outer
left mouse
shell) electrons are used in
sigma bonding. The other button and drag
electron is in a 'p' orbital which to get a different
can overlap laterally with view.
Electrical conductor neighbouring 'p' orbitals making
giant molecular pi orbitals that
extend over the whole of each (if you can't see
layer. Electrons are free to move the image you
within these delocalised pi have to
orbitals.
download chime)

There are only very weak Van

der Waal's attractions between
the carbon atoms and the water
Insoluble in water.
molecules whereas the carbon
atoms are bonded very tightly to
one another.

Many strong covalent bonds

holding the layers together - it
V. high melting point
requires massive amounts of
energy to pull it apart

Fullerenes

These are small molecules of carbon in which the giant structure is closed over into spheres
of atoms (bucky balls) or tubes (sometimes caled nano-tubes). The smallest fullerene has
60 carbon atoms arranged in pentagons and hexagons like a football. This is called
Buckminsterfullerene.

60
The name 'buckminster fullerene' comes from the inventor of the geodhesic dome (Richard
Buckminster Fuller) which has a similar structure to a fullerene. Fullerenes were first isolated
from the soot of chimineys and extracted from solvents as red crystals.

The bonding has delocalised pi molecular orbitals extending throughout the structure and
the carbon atoms are a mixture of sp2 and sp3 hybridised systems.

Fullerenes are insoluble in water but soluble in methyl benzene. They are non- conductors
as the individual molecules are only held to each other by weak van der Waal's forces.

Buckminster fullerene Structure

As the molecule is totally

symmetrical with all bond
lengths and angles being equal,
it is likely/inevitable that the
hybridisation of the carbon
atoms is somewhere between
that of sp2 and sp3. Another
example of a theory
(hybridisation in this case)
having to be modified to
accomodate the observed
experimental data.

Physical properties of fullerenes explained by considering the structure and bonding

Property Explanation Fullerene structure

Few covalent bonds holding the

molecules together but only
Soft and slippery
weak Vander Waals forces
between molecules.
Click on the
image with the
Soft weak crystals typical of
Brittle left mouse
covalent substances
button and drag

No movement of electrons to get a different

available from one molecule to view.
the next. The exception could be
the formation of nano-tubes that
Electrical insulator (if you can't see
are capable of conducting
electricity along their length. the image you
These are the subject of some have to
experiments in micro electronics
download chime)

There are only very weak Van

Insoluble in water. der Waal's attractions between
the carbon atoms and the water

61
 molecules whereas the carbon
atoms are bonded very tightly to
one another in the molecules.

Typical of covalent crystals

where only Van der Waal's
Low m.p. solids
interactions have to be broken
for melting.

Need a little help with this topic?

Why not try out the new interactive ebook on Bonding and Structure?

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Structures of carbon allotropes

Fullerenes

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