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DEFINITIONS OF OXIDATION AND REDUCTION (REDOX)

This page looks at the various definitions of oxidation and reduction (redox) in terms of the
transfer of oxygen, hydrogen and electrons. It also explains the terms oxidising agent and
reducing agent.

Oxidation and reduction in terms of oxygen transfer


Definitions

Oxidation is gain of oxygen.

Reduction is loss of oxygen.

For example, in the extraction of iron from its ore:

Because both reduction and oxidation are going on side-by-side, this is known as
a redox reaction.
Oxidising and reducing agents
An oxidising agent is substance which oxidises something else. In the above example, the
iron(III) oxide is the oxidising agent.
A reducing agent reduces something else. In the equation, the carbon monoxide is the
reducing agent.

Oxidising agents give oxygen to another substance.

Reducing agents remove oxygen from another substance.

Oxidation and reduction in terms of hydrogen transfer


These are old definitions which aren't used very much nowadays. The most likely place
you will come across them is in organic chemistry.
Definitions

Oxidation is loss of hydrogen.

Reduction is gain of hydrogen.

Notice that these are exactly the opposite of the oxygen definitions.
For example, ethanol can be oxidised to ethanal:

You would need to use an oxidising agent to remove the hydrogen from the ethanol. A
commonly used oxidising agent is potassium dichromate(VI) solution acidified with dilute
sulphuric acid.
Note: The equation for this is rather complicated for this introductory page. If you are
interested, you will find a similar example (ethanol to ethanoic acid) on the page dealing
withwriting equations for redox reactions.

Ethanal can also be reduced back to ethanol again by adding hydrogen to it. A possible
reducing agent is sodium tetrahydridoborate, NaBH 4. Again the equation is too complicated
to be worth bothering about at this point.

An update on oxidising and reducing agents

Oxidising agents give oxygen to another substance or remove hydrogen from it.

Reducing agents remove oxygen from another substance or give hydrogen to it.

Oxidation and reduction in terms of electron transfer


This is easily the most important use of the terms oxidation and reduction at A' level.
Definitions

Oxidation is loss of electrons.

Reduction is gain of electrons.

It is essential that you remember these definitions. There is a very easy way to do this. As
long as you remember that you are talking about electron transfer:

A simple example
The equation shows a simple redox reaction which can obviously be described in terms of
oxygen transfer.

Copper(II) oxide and magnesium oxide are both ionic. The metals obviously aren't. If you
rewrite this as an ionic equation, it turns out that the oxide ions are spectator ions and you

are left with:

A last comment on oxidising and reducing agents


If you look at the equation above, the magnesium is reducing the copper(II) ions by giving
them electrons to neutralise the charge. Magnesium is a reducing agent.
Looking at it the other way round, the copper(II) ions are removing electrons from the
magnesium to create the magnesium ions. The copper(II) ions are acting as an oxidising
agent.
Warning!
This is potentially very confusing if you try to learn both what oxidation and reduction mean
in terms of electron transfer, and also learn definitions of oxidising and reducing agents in
the same terms.
Personally, I would recommend that you work it out if you need it. The argument (going on
inside your head) would go like this if you wanted to know, for example, what an oxidising
agent did in terms of electrons:

An oxidising agent oxidises something else.

Oxidation is loss of electrons (OIL RIG).

That means that an oxidising agent takes electrons from that other substance.

So an oxidising agent must gain electrons.

Or you could think it out like this:

An oxidising agent oxidises something else.

That means that the oxidising agent must be being reduced.

Reduction is gain of electrons (OIL RIG).

So an oxidising agent must gain electrons.

Understanding is a lot safer than thoughtless learning!

WRITING IONIC EQUATIONS FOR REDOX REACTIONS

This page explains how to work out electron-half-reactions for oxidation and reduction
processes, and then how to combine them to give the overall ionic equation for a redox
reaction. This is an important skill in inorganic chemistry.
Don't worry if it seems to take you a long time in the early stages. It is a fairly slow process
even with experience. Take your time and practise as much as you can.

Electron-half-equations
What is an electron-half-equation?
When magnesium reduces hot copper(II) oxide to copper, the ionic equation for the
reaction is:

Note: I am going to leave out state symbols in all the equations on this page. This topic is
awkward enough anyway without having to worry about state symbols as well as everything else.
Practice getting the equations right, and then add the state symbols in afterwards if your

examiners are likely to want them.


How do you know whether your examiners will want you to include them? The best way is to look
at their mark schemes. You should be able to get these from your examiners' website. There are
links on the syllabuses page for students studying for UK-based exams.

You can split the ionic equation into two parts, and look at it from the point of view of the
magnesium and of the copper(II) ions separately. This shows clearly that the magnesium
has lost two electrons, and the copper(II) ions have gained them.

These two equations are described as "electron-half-equations" or "half-equations" or


"ionic-half-equations" or "half-reactions" - lots of variations all meaning exactly the same
thing!
Any redox reaction is made up of two half-reactions: in one of them electrons are being lost
(an oxidation process) and in the other one those electrons are being gained (a reduction
process).
Note: If you aren't happy about redox reactions in terms of electron transfer, you MUST read
the introductory page on redox reactions before you go on.

Working out electron-half-equations and using them to build ionic equations


In the example above, we've got at the electron-half-equations by starting from the ionic
equation and extracting the individual half-reactions from it. That's doing everything entirely
the wrong way round!
In reality, you almost always start from the electron-half-equations and use them to build
the ionic equation.

Example 1: The reaction between chlorine and iron(II) ions


Chlorine gas oxidises iron(II) ions to iron(III) ions. In the process, the chlorine is reduced to
chloride ions.
You would have to know this, or be told it by an examiner. In building equations, there is
quite a lot that you can work out as you go along, but you have to have somewhere to start
from!
You start by writing down what you know for each of the half-reactions. In the chlorine
case, you know that chlorine (as molecules) turns into chloride ions:

The first thing to do is to balance the atoms that you have got as far as you possibly can:

ALWAYS check that you have the existing atoms balanced before you do anything else. If
you forget to do this, everything else that you do afterwards is a complete waste of time!
Now you have to add things to the half-equation in order to make it balance completely.
All you are allowed to add are:

electrons

water

hydrogen ions (unless the reaction is being done under alkaline conditions - in
which case, you can add hydroxide ions instead)

In the chlorine case, all that is wrong with the existing equation that we've produced so far
is that the charges don't balance. The left-hand side of the equation has no charge, but the
right-hand side carries 2 negative charges.
That's easily put right by adding two electrons to the left-hand side. The final version of the
half-reaction is:

Now you repeat this for the iron(II) ions. You know (or are told) that they are oxidised to
iron(III) ions. Write this down:

The atoms balance, but the charges don't. There are 3 positive charges on the right-hand
side, but only 2 on the left.
You need to reduce the number of positive charges on the right-hand side. That's easily
done by adding an electron to that side:

Combining the half-reactions to make the ionic equation for the reaction
What we've got at the moment is this:

It is obvious that the iron reaction will have to happen twice for every chlorine molecule that
reacts. Allow for that, and then add the two half-equations together.

But don't stop there!! Check that everything balances - atoms and charges. It is very easy
to make small mistakes, especially if you are trying to multiply and add up more
complicated equations.

You will notice that I haven't bothered to include the electrons in the added-up version. If
you think about it, there are bound to be the same number on each side of the final
equation, and so they will cancel out. If you aren't happy with this, write them down and
then cross them out afterwards!

Example 2: The reaction between hydrogen peroxide and manganate(VII) ions


The first example was a simple bit of chemistry which you may well have come across. The
technique works just as well for more complicated (and perhaps unfamiliar) chemistry.
Manganate(VII) ions, MnO4-, oxidise hydrogen peroxide, H2O2, to oxygen gas. The reaction
is done with potassium manganate(VII) solution and hydrogen peroxide solution acidified
with dilute sulphuric acid.
During the reaction, the manganate(VII) ions are reduced to manganese(II) ions.
Let's start with the hydrogen peroxide half-equation. What we know is:

The oxygen is already balanced. What about the hydrogen?


All you are allowed to add to this equation are water, hydrogen ions and electrons. If you
add water to supply the extra hydrogen atoms needed on the right-hand side, you will mess
up the oxygens again - that's obviously wrong!
Add two hydrogen ions to the right-hand side.

Now all you need to do is balance the charges. You would have to add 2 electrons to the
right-hand side to make the overall charge on both sides zero.

Now for the manganate(VII) half-equation:

You know (or are told) that the manganate(VII) ions turn into manganese(II) ions. Write that
down.

The manganese balances, but you need four oxygens on the right-hand side. These can
only come from water - that's the only oxygen-containing thing you are allowed to write into
one of these equations in acid conditions.

By doing this, we've introduced some hydrogens. To balance these, you will need 8
hydrogen ions on the left-hand side.

Now that all the atoms are balanced, all you need to do is balance the charges. At the
moment there are a net 7+ charges on the left-hand side (1- and 8+), but only 2+ on the
right. Add 5 electrons to the left-hand side to reduce the 7+ to 2+.

This is the typical sort of half-equation which you will have to be able to work out. The
sequence is usually:

Balance the atoms apart from oxygen and hydrogen.

Balance the oxygens by adding water molecules.

Balance the hydrogens by adding hydrogen ions.

Balance the charges by adding electrons.

Combining the half-reactions to make the ionic equation for the reaction
The two half-equations we've produced are:

You have to multiply the equations so that the same number of electrons are involved in
both. In this case, everything would work out well if you transferred 10 electrons.

But this time, you haven't quite finished. During the checking of the balancing, you should
notice that there are hydrogen ions on both sides of the equation:

You can simplify this down by subtracting 10 hydrogen ions from both sides to leave the
final version of the ionic equation - but don't forget to check the balancing of the atoms and
charges!

You will often find that hydrogen ions or water molecules appear on both sides of the ionic
equation in complicated cases built up in this way. Always check, and then simplify where
possible.

Example 3: The oxidation of ethanol by acidified potassium dichromate(VI)


This technique can be used just as well in examples involving organic chemicals.
Potassium dichromate(VI) solution acidified with dilute sulphuric acid is used to oxidise

ethanol, CH3CH2OH, to ethanoic acid, CH3COOH.


The oxidising agent is the dichromate(VI) ion, Cr2O72-. This is reduced to chromium(III)
ions, Cr3+.
We'll do the ethanol to ethanoic acid half-equation first. Using the same stages as before,
start by writing down what you know:

Balance the oxygens by adding a water molecule to the left-hand side:

Add hydrogen ions to the right-hand side to balance the hydrogens:

And finally balance the charges by adding 4 electrons to the right-hand side to give an
overall zero charge on each side:

The dichromate(VI) half-equation contains a trap which lots of people fall into!
Start by writing down what you know:

What people often forget to do at this stage is to balance the chromiums. If you don't do
that, you are doomed to getting the wrong answer at the end of the process! When you
come to balance the charges you will have to write in the wrong number of electrons which means that your multiplying factors will be wrong when you come to add the halfequations . . . A complete waste of time!

Now balance the oxygens by adding water molecules . . .

. . . and the hydrogens by adding hydrogen ions:

Now all that needs balancing is the charges. Add 6 electrons to the left-hand side to give a
net 6+ on each side.

Combining the half-reactions to make the ionic equation for the reaction
What we have so far is:

What are the multiplying factors for the equations this time? The simplest way of working
this out is to find the smallest number of electrons which both 4 and 6 will divide into - in
this case, 12. That means that you can multiply one equation by 3 and the other by 2.
Note: Don't worry too much if you get this wrong and choose to transfer 24 electrons instead. All
that will happen is that your final equation will end up with everything multiplied by 2. Your
examiners might well allow that.

The multiplication and addition looks like this:

Now you will find that there are water molecules and hydrogen ions occurring on both sides
of the ionic equation. You can simplify this to give the final equation:

Note: You have now seen a cross-section of the sort of equations which you could be asked to
work out. Now you need to practice so that you can do this reasonably quickly and very
accurately! Aim to get an averagely complicated example done in about 3 minutes.
If you want a few more examples, and the opportunity to practice with answers available, you
might be interested in looking in chapter 1 of my book on Chemistry Calculations.

Reactions done under alkaline conditions


Working out half-equations for reactions in alkaline solution is decidedly more tricky than
those above. You are less likely to be asked to do this at this level (UK A level and its
equivalents), and for that reason I've covered these on a separate page (link below). It
would be worthwhile checking your syllabus and past papers before you start worrying
about these!

OXIDATION STATES (OXIDATION NUMBERS)

This page explains what oxidation states (oxidation numbers) are and how to
calculate them and make use of them.
Oxidation states are straightforward to work out and to use, but it is quite difficult to
define what they are in any quick way.

Explaining what oxidation states (oxidation numbers) are


Oxidation states simplify the whole process of working out what is being oxidised

and what is being reduced in redox reactions. However, for the purposes of this
introduction, it would be helpful if you knew about:

oxidation and reduction in terms of electron transfer

electron-half-equations
Note: If you aren't sure about either of these things, you might want to look at the pages
on redox definitions andelectron-half-equations. It would probably be best to read on and
come back to these links if you feel you need to.

We are going to look at some examples from vanadium chemistry. If you don't know
anything about vanadium, it doesn't matter in the slightest.
Vanadium forms a number of different ions - for example, V 2+and V3+. If you think about
how these might be produced from vanadium metal, the 2+ ion will be formed by oxidising
the metal by removing two electrons:

The vanadium is now said to be in an oxidation state of +2.


Removal of another electron gives the V3+ ion:

The vanadium now has an oxidation state of +3.


Removal of another electron gives a more unusual looking ion, VO 2+.

The vanadium is now in an oxidation state of +4. Notice that the oxidation state isn't simply
counting the charge on the ion (that was true for the first two cases but not for this one).
The positive oxidation state is counting the total number of electrons which have had to be
removed - starting from the element.

It is also possible to remove a fifth electron to give another ion (easily confused with the
one before!). The oxidation state of the vanadium is now +5.

Every time you oxidise the vanadium by removing another electron from it, its oxidation
state increases by 1.
Fairly obviously, if you start adding electrons again the oxidation state will fall. You could
eventually get back to the element vanadium which would have an oxidation state of zero.
What if you kept on adding electrons to the element? You can't actually do that with
vanadium, but you can with an element like sulphur.

The sulphur has an oxidation state of -2.


Summary
Oxidation state shows the total number of electrons which have been removed from an
element (a positive oxidation state) or added to an element (a negative oxidation state) to
get to its present state.
Oxidation involves an increase in oxidation state
Reduction involves a decrease in oxidation state
Recognising this simple pattern is the single most important thing about the concept of
oxidation states. If you know how the oxidation state of an element changes during a
reaction, you can instantly tell whether it is being oxidised or reduced without having to
work in terms of electron-half-equations and electron transfers.

Working out oxidation states


You don't work out oxidation states by counting the numbers of electrons transferred. It
would take far too long. Instead you learn some simple rules, and do some very simple

sums!

The oxidation state of an uncombined element is zero. That's obviously so, because
it hasn't been either oxidised or reduced yet! This applies whatever the structure of
the element - whether it is, for example, Xe or Cl 2 or S8, or whether it has a giant
structure like carbon or silicon.

The sum of the oxidation states of all the atoms or ions in a neutral compound is
zero.

The sum of the oxidation states of all the atoms in an ion is equal to the charge on
the ion.

The more electronegative element in a substance is given a negative oxidation


state. The less electronegative one is given a positive oxidation state. Remember
that fluorine is the most electronegative element with oxygen second.

Some elements almost always have the same oxidation states in their compounds:
element

usual oxidation state

exceptions

Group 1 metals

always +1

Group 2 metals

always +2

Oxygen

usually -2

except in peroxides and F2O (see


below)

Hydrogen

usually +1

except in metal hydrides where it is -1


(see below)

Fluorine

always -1

Chlorine

usually -1

except in compounds with O or F (see


below)

The reasons for the exceptions


Hydrogen in the metal hydrides
Metal hydrides include compounds like sodium hydride, NaH. In this, the hydrogen is
present as a hydride ion, H-. The oxidation state of a simple ion like hydride is equal to the
charge on the ion - in this case, -1.
Alternatively, you can think of it that the sum of the oxidation states in a neutral compound
is zero. Since Group 1 metals always have an oxidation state of +1 in their compounds, it
follows that the hydrogen must have an oxidation state of -1 (+1 -1 = 0).
Oxygen in peroxides
Peroxides include hydrogen peroxide, H2O2. This is an electrically neutral compound and
so the sum of the oxidation states of the hydrogen and oxygen must be zero.
Since each hydrogen has an oxidation state of +1, each oxygen must have an oxidation
state of -1 to balance it.
Oxygen in F2O
The problem here is that oxygen isn't the most electronegative element. The fluorine is
more electronegative and has an oxidation state of -1. In this case, the oxygen has an
oxidation state of +2.
Chlorine in compounds with fluorine or oxygen
There are so many different oxidation states that chlorine can have in these, that it is safer
to simply remember that the chlorine doesn't have an oxidation state of -1 in them, and
work out its actual oxidation state when you need it. You will find an example of this below.

Warning!
Don't get too bogged down in these exceptions. In most of the cases you will come across,
they don't apply!

Examples of working out oxidation states


What is the oxidation state of chromium in Cr2+?
That's easy! For a simple ion like this, the oxidation state is the charge on the ion - in other
words: +2 (Don't forget the + sign.)
What is the oxidation state of chromium in CrCl 3?
This is a neutral compound so the sum of the oxidation states is zero. Chlorine has an
oxidation state of -1. If the oxidation state of chromium is n:
n + 3(-1) = 0
n = +3 (Again, don't forget the + sign!)
What is the oxidation state of chromium in Cr(H 2O)63+?
This is an ion and so the sum of the oxidation states is equal to the charge on the ion.
There is a short-cut for working out oxidation states in complex ions like this where the
metal atom is surrounded by electrically neutral molecules like water or ammonia.
The sum of the oxidation states in the attached neutral molecule must be zero. That means
that you can ignore them when you do the sum. This would be essentially the same as an
unattached chromium ion, Cr3+. The oxidation state is +3.
What is the oxidation state of chromium in the dichromate ion, Cr 2O72-?
The oxidation state of the oxygen is -2, and the sum of the oxidation states is equal to the
charge on the ion. Don't forget that there are 2 chromium atoms present.
2n + 7(-2) = -2
n = +6
Warning: Because these are simple sums it is tempting to try to do them in your head. If
it matters (like in an exam) write them down using as many steps as you need so that
there is no chance of making careless mistakes. Your examiners aren't going to be
impressed by your mental arithmetic - all they want is the right answer!

If you want some more examples to practice on, you will find them in most text books,
including my chemistry calculations book.

What is the oxidation state of copper in CuSO 4?


Unfortunately, it isn't always possible to work out oxidation states by a simple use of the
rules above. The problem in this case is that the compound contains two elements (the
copper and the sulphur) whose oxidation states can both change.
The only way around this is to know some simple chemistry! There are two ways you might
approach it. (There might be others as well, but I can't think of them at the moment!)

You might recognise this as an ionic compound containing copper ions and sulphate
ions, SO42-. To make an electrically neutral compound, the copper must be present
as a 2+ ion. The oxidation state is therefore +2.

You might recognise the formula as being copper(II) sulphate. The "(II)" in the name
tells you that the oxidation state is 2 (see below).
You will know that it is +2 because you know that metals form positive ions, and the
oxidation state will simply be the charge on the ion.

Using oxidation states


In naming compounds
You will have come across names like iron(II) sulphate and iron(III) chloride. The (II) and
(III) are the oxidation states of the iron in the two compounds: +2 and +3 respectively. That
tells you that they contain Fe2+ and Fe3+ ions.
This can also be extended to the negative ion. Iron(II) sulphate is FeSO 4. There is also a
compound FeSO3 with the old name of iron(II) sulphite. The modern names reflect the
oxidation states of the sulphur in the two compounds.
The sulphate ion is SO42-. The oxidation state of the sulphur is +6 (work it out!). The ion is

more properly called the sulphate(VI) ion.


The sulphite ion is SO32-. The oxidation state of the sulphur is +4 (work that out as well!).
This ion is more properly called the sulphate(IV) ion. The ate ending simply shows that the
sulphur is in a negative ion.
So FeSO4 is properly called iron(II) sulphate(VI), and FeSO 3 is iron(II) sulphate(IV). In fact,
because of the easy confusion between these names, the old names sulphate and sulphite
are normally still used in introductory chemistry courses.
Note: Even these aren't the full name! The oxygens in the negative ions should also be
identified. FeSO4 is properly called iron(II) tetraoxosulphate(VI). It all gets a bit out of
hand for everyday use for common ions.

Using oxidation states to identify what's been oxidised and what's been reduced
This is easily the most common use of oxidation states.
Remember:
Oxidation involves an increase in oxidation state
Reduction involves a decrease in oxidation state
In each of the following examples, we have to decide whether the reaction involves redox,
and if so what has been oxidised and what reduced.
Example 1:
This is the reaction between magnesium and hydrochloric acid or hydrogen chloride gas:

Have the oxidation states of anything changed? Yes they have - you have two elements
which are in compounds on one side of the equation and as uncombined elements on the

other. Check all the oxidation states to be sure:.

The magnesium's oxidation state has increased - it has been oxidised. The hydrogen's
oxidation state has fallen - it has been reduced. The chlorine is in the same oxidation state
on both sides of the equation - it hasn't been oxidised or reduced.
Example 2:
The reaction between sodium hydroxide and hydrochloric acid is:

Checking all the oxidation states:

Nothing has changed. This isn't a redox reaction.


Example 3:
This is a sneaky one! The reaction between chlorine and cold dilute sodium hydroxide
solution is:

Obviously the chlorine has changed oxidation state because it has ended up in compounds
starting from the original element. Checking all the oxidation states shows:

The chlorine is the only thing to have changed oxidation state. Has it been oxidised or
reduced? Yes! Both! One atom has been reduced because its oxidation state has fallen.
The other has been oxidised.
This is a good example of a disproportionation reaction. A disproportionation reaction is
one in which a single substance is both oxidised and reduced.

Using oxidation states to work out reacting proportions


This is sometimes useful where you have to work out reacting proportions for use in
titration reactions where you don't have enough information to work out the complete ionic
equation.
Remember that each time an oxidation state changes by one unit, one electron has been
transferred. If one substance's oxidation state in a reaction falls by 2, that means that it has
gained 2 electrons.
Something else in the reaction must be losing those electrons. Any oxidation state fall by
one substance must be accompanied by an equal oxidation state increase by something
else.

This example is based on information in an old AQA A' level question.


Ions containing cerium in the +4 oxidation state are oxidising agents. (They are more
complicated than just Ce4+.) They can oxidise ions containing molybdenum from the +2 to
the +6 oxidation state (from Mo2+ to MoO42-). In the process the cerium is reduced to the +3
oxidation state (Ce3+). What are the reacting proportions?
The oxidation state of the molybdenum is increasing by 4. That means that the oxidation

state of the cerium must fall by 4 to compensate.


But the oxidation state of the cerium in each of its ions only falls from +4 to +3 - a fall of 1.
So there must obviously be 4 cerium ions involved for each molybdenum ion.
The reacting proportions are 4 cerium-containing ions to 1 molybdenum ion.

Or to take a more common example involving iron(II) ions and manganate(VII) ions . . .
A solution of potassium manganate(VII), KMnO 4, acidified with dilute sulphuric acid
oxidises iron(II) ions to iron(III) ions. In the process, the manganate(VII) ions are reduced to
manganese(II) ions. Use oxidation states to work out the equation for the reaction.
The oxidation state of the manganese in the manganate(VII) ion is +7. The name tells you
that, but work it out again just for the practice!
In going to manganese(II) ions, the oxidation state of manganese has fallen by 5. Every
iron(II) ion that reacts, increases its oxidation state by 1. That means that there must be
five iron(II) ions reacting for every one manganate(VII) ion.
The left-hand side of the equation will therefore be: MnO 4- + 5Fe2+ + ?
The right-hand side will be: Mn2+ + 5Fe3+ + ?
After that you will have to make guesses as to how to balance the remaining atoms and the
charges. In this case, for example, it is quite likely that the oxygen will end up in water. That
means that you need some hydrogen from somewhere.
That isn't a problem because you have the reaction in acid solution, so the hydrogens
could well come from hydrogen ions.
Eventually, you will end up with this:

Personally, I would much rather work out these equations from electron-half-equations!
TOMIC AND PHYSICAL PROPERTIES OF THE GROUP 1 ELEMENTS

This page explores the trends in some atomic and physical properties of the
Group 1 elements - lithium, sodium, potassium, rubidium and caesium. You will
find separate sections below covering the trends in atomic radius, first
ionisation energy, electronegativity, melting and boiling points, and density.
Even if you aren't currently interested in all these things, it would probably
pay you to read the whole page. The same ideas tend to recur throughout the
atomic properties, and you may find that earlier explanations help to you
understand later ones.
Trends in Atomic Radius
Note: You will find atomic radius covered in detail in another part of this
site. If you choose to follow this link, use the BACK button on your browser
to return quickly to this page.

You can see that the atomic radius increases as you go down the Group.
Explaining the increase in atomic radius
The radius of an atom is governed by

the number of layers of electrons around the nucleus

the pull the outer electrons feel from the nucleus.

Compare lithium and sodium:


Li

1s22s1

Na

1s22s22p63s1

Note: If you aren't sure about writing electronic structures using s and p
notation it might be a good idea to follow this link before you go on. Use
the BACK button on your browser to return quickly to this page.

In each case, the outer electron feels a net pull of 1+ from the nucleus. The positive charge
on the nucleus is cut down by the negativeness of the inner electrons.

This is equally true for all the other atoms in Group 1. Work it out for potassium if you aren't
convinced.
The only factor which is going to affect the size of the atom is therefore the number of
layers of inner electrons which have to be fitted in around the atom. Obviously, the more
layers of electrons you have, the more space they will take up - electrons repel each other.
That means that the atoms are bound to get bigger as you go down the Group.
Note: You may think that this is all a bit long-winded! It is, after all, fairly
obvious that atoms will get bigger if you add more layers of electrons. Why,
then, bother about exploring the net pull on the electrons from the centre
of the atom?
It is a matter of setting up good habits. If you are talking about atoms in the
same Group, the net pull from the centre will always be the same - and
you could ignore it without creating problems. That isn't true if you try to
compare atoms from different parts of the Periodic Table. If you don't get
into the habit of thinking about all the possible factors, you are going to
make mistakes.

Trends in First Ionisation Energy


First ionisation energy is the energy needed to remove the most loosely held electron from
each of one mole of gaseous atoms to make one mole of singly charged gaseous ions - in
other words, for 1 mole of this process:

Note: You will find ionisation energy covered in detail in another part of
this site. If you choose to follow this link, use the BACK button on your
browser to return quickly to this page.

Notice that first ionisation energy falls as you go down the group.
Explaining the decrease in first ionisation energy
Ionisation energy is governed by

the charge on the nucleus,

the amount of screening by the inner electrons,

the distance between the outer electrons and the nucleus.

As you go down the Group, the increase in nuclear charge is exactly offset by the increase

in the number of inner electrons. Just as when we were talking about atomic radius further
up this page, in each of the elements in this Group, the outer electrons feel a net attraction
of 1+ from the centre.
However, as you go down the Group, the distance between the nucleus and the outer
electrons increases and so they become easier to remove - the ionisation energy falls.

Trends in Electronegativity
Electronegativity is a measure of the tendency of an atom to attract a bonding pair of
electrons. It is usually measured on the Pauling scale, on which the most electronegative
element (fluorine) is given an electronegativity of 4.0.
Note: You will find electronegativity covered in detail in another part of
this site. If you choose to follow this link, use the BACK button on your
browser to return quickly to this page.

All of these elements have a very low electronegativity. (Remember that the most
electronegative element, fluorine, has an electronegativity of 4.0.) Notice that
electronegativity falls as you go down the Group. The atoms become less and less good at
attracting bonding pairs of electrons.
Note: You might argue that the fall doesn't apply throughout the Group
because both potassium and rubidium have an electronegativity of 0.8.

This can't be explained just as a rounding error (as I have done elsewhere
on the site in thecorresponding Group 2 case), because both elements
have the same electronegativity to 2 decimal places as well. Both are 0.82.
I'm not clear what the reason for this is! There are various other measures
of electronegativity apart from the Pauling one, and on each of these the
rubidium value is indeed smaller than the potassium one.

Explaining the decrease in electronegativity


Imagine a bond between a sodium atom and a chlorine atom. Think of it to start with as a
covalent bond - a pair of shared electrons. The electron pair will be dragged towards the
chlorine because there is a much greater net pull from the chlorine nucleus than from the
sodium one.

The electron pair ends up so close to the chlorine that there is essentially a transfer of an
electron to the chlorine - ions are formed.
The large pull from the chlorine nucleus is why chlorine is much more electronegative than
sodium is.
Now compare this with the lithium-chlorine bond.
The net pull from each end of the bond is the same as before, but you have to remember
that the lithium atom is smaller than a sodium atom. That means that the electron pair is
going to be closer to the net 1+ charge from the lithium end, and so more strongly attracted

to it.

In some lithium compounds there is often a degree of covalent bonding that isn't there in
the rest of the Group. Lithium iodide, for example, will dissolve in organic solvents - a
typical property of covalent compounds. The iodine atom is so large that the pull from the
iodine nucleus on the pair of electrons is relatively weak, and so a fully ionic bond isn't
formed.
Summarising the trend down the Group
As the metal atoms get bigger, any bonding pair gets further and further away from the
metal nucleus, and so is less strongly attracted towards it. In other words, as you go down
the Group, the elements become less electronegative.
With the exception of some lithium compounds, these elements all form compounds which
we consider as being fully ionic. They are so weakly electronegative that we assume that
the electron pair is pulled so far away towards the chlorine (or whatever) that ions are
formed.

Trends in Melting and Boiling Points

You will see that both the melting points and boiling points fall as you go down the Group.
Explaining the trends in melting and boiling points
When you melt any of these metals, the metallic bond is weakened enough for the atoms
to move around, and is then broken completely when you boil the metal.
The fall in melting and boiling points reflects the fall in the strength of the metallic bond.
Note: If you aren't confident about metallic bonding you should follow this
link before you go on. Use the BACK button on your browser to return
quickly to this page.

The atoms in a metal are held together by the attraction of the nuclei to the delocalised
electrons. As the atoms get bigger, the nuclei get further away from these delocalised
electrons, and so the attractions fall. That means that the atoms are more easily pulled
apart to make a liquid and finally a gas.
In the same way that we have already discussed, each of these atoms has a net pull from
the nuclei of 1+. The increased charge on the nucleus as you go down the Group is offset
by additional levels of screening electrons. All that matters is the distance between the
nucleus and the bonding electrons.
Note: This explanation seems fairly obvious, and works well for the Group

1 metals. However, if you have read about thecorresponding Group 2


case, you will know that life isn't always so simple!

Trends in Density

Notice that these are all light metals - and that the first three in the Group are less dense
than water (less than 1 g cm-3). That means that the first three will float on water, while the
other two sink.
The density tends to increase as you go down the Group (apart from the fluctuation at
potassium).
Explaining the trend in density
It is quite difficult to come up with a simple explanation for this, because the density
depends on two factors, both of which are changing as you go down the Group.
All of these metals have their atoms packed in the same way, so all you have to consider is
how many atoms you can pack in a given volume, and what the mass of the individual
atoms is. How many you can pack depends, of course, on their volume - and their volume,
in turn, depends on their atomic radius.
As you go down the Group, the atomic radius increases, and so the volume of the atoms
increases as well. That means that you can't pack as many sodium atoms into a given

volume as you can lithium atoms.


However, as you go down the Group, the mass of the atoms increases. That means that a
particular number of sodium atoms will weigh more than the same number of lithium
atoms.
So 1 cm3 of sodium will contain fewer atoms than the same volume of lithium, but each
atom will weigh more. What affect will that have on the density? It is completely impossible
to say unless you do some sums!
Note: If your maths is reasonable, it isn't too difficult to work out what the
density of sodium should be if you know lithium's density and have figures
for relative atomic mass and atomic radius - and similarly all the rest of the
way down the Group. I'm not going to waste time and space doing it,
because I can't conceive of any situation when you would ever be asked to
do it! If you want to try it, you will find that the density is inversely
proportional to the volumes of the atoms and directly proportional to their
masses.

REACTIONS OF THE GROUP 1 ELEMENTS WITH


WATER
This page looks at the reactions of the Group 1 elements - lithium, sodium, potassium,
rubidium and caesium - with water. It uses these reactions to explore the trend in reactivity
in Group 1.

The Facts
General
All of these metals react vigorously or even explosively with cold water. In each case, a
solution of the metal hydroxide is produced together with hydrogen gas.

This equation applies to any of these metals and water - just replace the X by the symbol
you want.
In each of the following descriptions, I am assuming a very small bit of the metal is
dropped into water in a fairly large container.

Details for the individual metals


Lithium
Lithium's density is only about half that of water so it floats on the surface, gently fizzing
and giving off hydrogen. It gradually reacts and disappears, forming a colourless solution of
lithium hydroxide. The reaction generates heat too slowly and lithium's melting point is too
high for it to melt (see sodium below).
Sodium
Sodium also floats on the surface, but enough heat is given off to melt the sodium (sodium
has a lower melting point than lithium and the reaction produces heat faster) and it melts
almost at once to form a small silvery ball that dashes around the surface. A white trail of
sodium hydroxide is seen in the water under the sodium, but this soon dissolves to give a
colourless solution of sodium hydroxide.
The sodium moves because it is pushed around by the hydrogen which is given off during
the reaction. If the sodium becomes trapped on the side of the container, the hydrogen
may catch fire to burn with an orange flame. The colour is due to contamination of the
normally blue hydrogen flame with sodium compounds.
Potassium
Potassium behaves rather like sodium except that the reaction is faster and enough heat is
given off to set light to the hydrogen. This time the normal hydrogen flame is contaminated
by potassium compounds and so is coloured lilac (a faintly bluish pink).

Rubidium
Rubidium is denser than water and so sinks. It reacts violently and immediately, with
everything spitting out of the container again. Rubidium hydroxide solution and hydrogen
are formed.
Caesium
Caesium explodes on contact with water, quite possibly shattering the container. Caesium
hydroxide and hydrogen are formed

Summary of the trend in reactivity


The Group 1 metals become more reactive towards water as you go down the Group.

Explaining the trend in reactivity


Looking at the enthalpy changes for the reactions
The overall enthalpy changes
You might think that because the reactions get more dramatic as you go down the Group,
the amount of heat given off increases as you go from lithium to caesium. Not so!
The table gives estimates of the enthalpy change for each of the elements undergoing the
reaction:

Note: That's the same equation as before, but I have divided it by two
to show the enthalpy change per mole of metal reacting.

enthalpy change (kJ / mol)


Li

-222

Na

-184

-196

Rb

-195

Cs

-203

You will see that there is no pattern at all in these values. They are all fairly similar and,
surprisingly, lithium is the metal which releases the most heat during the reaction!
Note: Apart from the lithium value, I haven't been able to confirm these
figures. For lithium, sodium and potassium, they are calculated values
based on information in the Nuffield Advanced Science Book of Data
(page 114 of my 1984 edition). The lithium value agrees almost exactly
with a value I found during a web search. The values for rubidium and
caesium are calculated indirectly from the Li, Na and K values and other
information which you will find in a later table on this page.

Digging around in the enthalpy changes


When these reactions happen, the differences between them lie entirely in what is
happening to the metal atoms present. In each case, you start with metal atoms in a solid
and end up with metal ions in solution.
Overall, what happens to the metal is this:

You can calculate the overall enthalpy change for this process by using Hess's Law and

breaking it up into several steps that we know the enthalpy changes for.
First, you would need to supply atomisation energy to give gaseous atoms of the metal.

Then ionise the metal by supplying its first ionisation energy.

And finally, you would get hydration enthalpy released when the gaseous ion comes into
contact with water.

Note: There is no suggestion that the reaction actually happens by this


route. All we are doing is inventing an imaginary route from the start to
the end point of the reaction, and using Hess's Law to say that the
overall enthalpy change will be exactly the same as we can calculate
using this imaginary route. If you don't know about Hess's Law, you
probably aren't likely to be making much sense of all this bit of the page
anyway. If you aren't happy about enthalpy changes, you might want to
explore the energetics section of Chemguide, or my chemistry
calculations book.

If we put values for all these steps into a table, they look like this (all values in kJ / mol):
at. energy

1st IE

hydr. enthalpy

total

Li

+161

+519

-519

+161

Na

+109

+494

-406

+197

+90

+418

-322

+186

Rb

+86

+402

-301

+187

Cs

+79

+376

-276

+179

Note: Remember that these aren't the overall enthalpy changes for the
reactions when the metal reacts with water. They are only for that part of
the reaction which involves the metal. There are also changes going on
with the water present - turning it into hydrogen gas and hydroxide ions.
To get the total enthalpy changes, you would have to add these values
in as well.
The changes due to the water will, however, be the same for each
reaction - in each case about -382 kJ / mol. Adding that on to the figures
in this table gives the values in the previous one to within a kJ or two.
The rubidium and caesium values will agree exactly, because that's how
I had to calculate them in the first table. The other three in the previous
table were calculated from information from a different source.

So why isn't there any pattern in these values? If you look at the various bits of information,
you will find that as you go down the Group each of them decreases:

The atomisation energy is a measure of the strength of the metallic bond in each
element. This is falling as the atom gets bigger and the metallic bond is getting
longer. The delocalised electrons are further from the attraction of the nuclei in the
bigger atoms.

The first ionisation energy is falling because the electron being removed is getting
more distant from the nucleus. The extra protons in the nucleus are screened by
additional layers of electrons.

The hydration enthalpy is a measure of the attraction between the metal ions and
lone pairs on water molecules. As the ions get bigger, the water molecules are
further from the attraction of the nucleus. The extra protons in the nucleus are again
screened by the extra layers of electrons.

What is happening is that the various factors are falling at different rates. That destroys any
overall pattern.

It is, however, possible to look at the table again and find a pattern which is useful.

Looking at the activation energies for the reactions


Let's take the last table and just look at the energy input terms - the two processes where
you have to supply energy to make them work. In other words, we will miss out the
hydration enthalpy term and just add up the other two.
at. energy

1st IE

total

Li

+161

+519

+680

Na

+109

+494

+603

+90

+418

+508

Rb

+86

+402

+488

Cs

+79

+376

+455

Now you can see that there is a steady fall as you go down the Group. As you go from
lithium to caesium, you need to put less energy into the reaction to get a positive ion
formed. This energy will be recovered later on (plus quite a lot more!), but has to be
supplied initially. This is going to be related to the activation energy of the reaction.
The lower the activation energy, the faster the reaction.
So although lithium releases most heat during the reaction, it does it relatively slowly - it
isn't all released in one short, sharp burst. Caesium, on the other hand, has a significantly
lower activation energy, and so although it doesn't release quite as much heat overall, it
does it extremely quickly - and you get an explosion.
Note: You need to be a bit careful about how you phrase this! You
probably haven't noticed my use of the phrase "This is going to

be related to the activation energy of the reaction." In rewriting it, I have


emphasised the words "related to".
The reaction certainly won't involve exactly the energy terms we are
talking about. The metal won't first convert to gaseous atoms which then
lose an electron. But at some point, atoms will have to break away from
the metal structure and they will have to lose electrons.
However, other energy releasing processes may happen at exactly the
same time - for example, if the metal atom loses an electron, something
almost certainly picks it up simultaneously. The electron is never likely to
be totally free. That will have the effect of reducing the height of the real
activation energy barrier. The values we have calculated by adding up
the atomisation and ionisation energies are very big in activation energy
terms and the reactions would be extremely slow if they were for real.

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 in
part due to a decrease in ionisation energy as you go down the Group, and in part to a fall
in atomisation energy reflecting weaker metallic bonds as you go from lithium to caesium.
This leads to lower activation energies, and therefore faster reactions.
Note: If you are a UK A level student, you will almost certainly find that
your examiners will only expect you to explain this in terms of the fall in
ionisation energy as you go down the Group. In other words, they
simplify things by overlooking the contribution from atomisation energy.
Stick with what your examiners expect - don't make life difficult for
yourself! I'm trying to be as rigorous as I can because a sizeable part of
my audience is working in systems outside the UK or beyond A level.

REACTIONS OF THE GROUP 1 ELEMENTS WITH


OXYGEN AND CHLORINE
This page mainly looks at the reactions of the Group 1 elements (lithium, sodium,

potassium, rubidium and caesium) with oxygen - including the simple reactions of the
various kinds of oxides formed. It also deals very briefly with the reactions of the elements
with chlorine.

The Reactions with Air or Oxygen


General
These are all very reactive metals and have to be stored out of contact with air to prevent
their oxidation. Reactivity increases as you go down the Group.
Lithium, sodium and potassium are stored in oil. (Lithium in fact floats on the oil, but there
will be enough oil coating it to give it some protection. It is, anyway, less reactive than the
rest of the Group.)
Rubidium and caesium are normally stored in sealed glass tubes to prevent air getting at
them. They are stored either in a vacuum or in an inert atmosphere of, say, argon. The
tubes are broken open when the metal is used.
Depending on how far down the Group you are, different kinds of oxide are formed when
the metals burn (details below). Reaction with oxygen is just a more dramatic version of the
reaction with air.
Lithium is unique in the Group because it also reacts with the nitrogen in the air to form
lithium nitride (again, see below).

Details for the individual metals


Lithium
Lithium burns with a strongly red-tinged flame if heated in air. It reacts with oxygen in the
air to give white lithium oxide. With pure oxygen, the flame would simply be more intense.

For the record, it also reacts with the nitrogen in the air to give lithium nitride. Lithium is the

only element in this Group to form a nitride in this way.

Note: You will find the reason why lithium forms a nitride on the
page about reactions of Group 2 elements with air or oxygen.
You will find what you want about 3/4 of the way down that page.
Lithium's reactions are often rather like those of the Group 2
metals. There is a diagonal relationship between lithium and
magnesium. You will find this discussed on the page
aboutelectronegativity.
Use the BACK button on your browser to return to this page from
either of these links.

Sodium
Small pieces of sodium burn in air with often little more than an orange glow. Using larger
amounts of sodium or burning it in oxygen gives a strong orange flame. You get a white
solid mixture of sodium oxide and sodium peroxide.
The equation for the formation of the simple oxide is just like the lithium one.

The peroxide equation is:

Potassium
Small pieces of potassium heated in air tend to just melt and turn instantly into a mixture of
potassium peroxide and potassium superoxide without any flame being seen. Larger
pieces of potassium burn with a lilac flame.

The equation for the formation of the peroxide is just like the sodium one above:

. . . and for the superoxide:

Note: Potassium peroxide and superoxide are described as


being somewhere between yellow and orange depending on
what source you look at. I have a bit of a problem with this,
because over my teaching career I have heated potassium in air
many times and, if memory serves correctly, it always leaves a
greyish white film on the bit of porcelain you are heating it on. I
don't recall ever seeing it yellow or orange!
The formula for a peroxide doesn't look too stange, because
most people are familiar with the similar formula for hydrogen
peroxide. The formula for a superoxide always looks wrong!
There is more about these oxides later on.

Rubidium and caesium


Both metals catch fire in air and produce superoxides, RbO 2 and CsO2. The equations are
the same as the equivalent potassium one.
Note: In a lifetime in teaching chemistry, I have never actually
handled (or even seen in real life!) either of these metals. I
haven't even seen video or film clips of them being burnt. That
means that I don't have much confidence in this next bit.

Both superoxides are described in most sources as being either orange or yellow. One
major web source describes rubidium superoxide as being dark brown on one page and
orange on another!

I don't know what the flames look like either. You can't necessarily be sure that the flame
that a metal burns with will be the same as the flame colour of its compounds.

Why are different oxides formed as you go down the Group?

Lithium (and to some extent sodium) form simple oxides, X 2O, which contain the
common O2- ion.

Sodium (and to some extent potassium) form peroxides, X 2O2, containing the more
complicated O22- ion (discussed below).

Potassium, rubidium and caesium form superoxides, XO 2. The structure of the


superoxide ion, O2-, is too difficult to discuss at this level, needing a good knowledge
of molecular orbital theory to make sense of it.

The more complicated ions aren't stable in the presence of a small positive ion. Consider
the peroxide ion, for example.
The peroxide ion, O22- looks like this:

The covalent bond between the two oxygen atoms is relatively weak.
Now imagine bringing a small positive 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.

Even though it only has one charge, the lithium ion at the top of the Group is so small and
has such a high charge density that any peroxide ion near it falls to pieces to give an oxide
and oxygen. As you go down the Group to sodium and potassium the positive ions get
bigger and they don't have so much effect on the peroxide ion.
The superoxide ions are even more easily pulled apart, and these are only stable in the
presence of the big ions towards the bottom of the Group.
So why do any of the metals form the more complicated oxides? It is a matter of
energetics.
In the presence of sufficient oxygen, they produce the compound whose formation gives
out most energy. That gives the most stable compound.
The amount of heat evolved per mole of rubidium in forming its various oxides is:
enthalpy change (kJ / mol of Rb)
Rb2O

-169.5

Rb2O2

-236

RbO2

-278.7
Note: These figures are based on a thermodynamic properties
table from Gazi University in Turkey. It was the only place I could
track down a value for the enthalpy of formation of rubidium
superoxide. The enthalpy of formation values for rubidium oxide
and peroxide have been divided by two to give results per mole
of rubidium in order to make them comparable with the
superoxide value.

The values for the various potassium oxides show exactly the same trends. As long as you
have enough oxygen, forming the peroxide releases more energy per mole of metal than
forming the simple oxide. Forming the superoxide releases even more.
I assume the same thing to be true of the caesium oxides, although I couldn't find all the
figures to be able to check it.

Summary
Forming the more complicated oxides from the metals releases more energy and makes
the system more energetically stable. BUT . . . this only works for the metals in the lower
half of the Group where the metal ions are big and have a low charge density.
At the top of the Group, the small ions with a higher charge density tend to polarise the
more complicated oxide ions to the point of destruction.

Reactions of the Oxides


The simple oxides, X2O
Reaction with water
These are simple basic oxides, reacting with water to give the metal hydroxide.

For example, lithium oxide reacts with water to give a colourless solution of lithium
hydroxide.

Note: I'm going to use "X" for all the rest of the equations in this
section. There is no difference between the equations for the
various elements in the Group whichever metal oxide (or
peroxide or superoxide) you are using.

Reaction with dilute acids


These simple oxides all react with an acid to give a salt and water. For example, sodium
oxide will react with dilute hydrochloric acid to give colourless sodium chloride solution and
water.

The peroxides, X2O2


Reaction with water
If the reaction is done ice cold (and the temperature controlled so that it doesn't rise even
though these reactions are strongly exothermic), a solution of the metal hydroxide and
hydrogen peroxide is formed.

If the temperature increases (as it inevitably will unless the peroxide is added to water very,
very, very slowly!), the hydrogen peroxide produced decomposes into water and oxygen.
The reaction can be very violent overall.

Reaction with dilute acids


These reactions are even more exothermic than the ones with water. A solution containing

a salt and hydrogen peroxide is formed. The hydrogen peroxide will decompose to give
water and oxygen if the temperature rises - again, it is almost impossible to avoid this.
Another potentially violent reaction!

The superoxides, XO2


Reaction with water
This time, a solution of the metal hydroxide and hydrogen peroxide is formed, but oxygen
gas is given off as well. Once again, these are strongly exothermic reactions and the heat
produced will inevitably decompose the hydrogen peroxide to water and more oxygen.
Again violent!

Reaction with dilute acids


Again, these reactions are even more exothermic than the ones with water. A solution
containing a salt and hydrogen peroxide is formed together with oxygen gas. The hydrogen
peroxide will again decompose to give water and oxygen as the temperature rises. Violent!

The Reactions of the elements with Chlorine


This is included on this page because of the similarity in appearance between the
reactions of the Group 1 metals with chlorine and with oxygen.
Sodium, for example, burns with an intense orange flame in chlorine in exactly the same
way that it does in pure oxygen. The rest also behave the same in both gases.
In each case, there is a white solid residue which is the simple chloride, XCl. There is

nothing in any way complicated about these reactions!

SOME COMPOUNDS OF THE GROUP 1 ELEMENTS

This page looks at some compounds of the Group 1 elements (lithium, sodium,
potassium, rubidium and caesium) - limited to various bits and pieces required by
various UK A level syllabuses. You will find some information about the nitrates,
carbonates, hydrogencarbonates and hydrides of the metals.
We will first look at what happens to some of the compounds on heating, and then
their solubility. At the end, you will find a section about the preparation and
reactions of the metal hydrides.

The effect of heat on Group 1 compounds


The facts
Group 1 compounds are more stable to heat than the corresponding compounds in
Group 2. You will often find that the lithium compounds behave similarly to Group 2
compounds, but the rest of Group 1 are in some way different.

Heating the nitrates


Most nitrates tend to decompose on heating to give the metal oxide, brown fumes of
nitrogen dioxide, and oxygen.
For example, a typical Group 2 nitrate like magnesium nitrate decomposes like this:

In Group 1, lithium nitrate behaves in the same way - producing lithium oxide,

nitrogen dioxide and oxygen.

The rest of the Group, however, don't decompose so completely (at least not at
Bunsen temperatures) - producing the metal nitrite and oxygen, but no nitrogen
dioxide.

All the nitrates from sodium to caesium decomposes in this same way, the only
difference being how hot they have to be to undergo the reaction. As you go down
the Group, the decomposition gets more difficult, and you have to use higher
temperatures.
Note: The more modern name for sodium nitrite is
sodium nitrate(III). On this basis, sodium nitrate should
properly be called sodium nitrate(V). Most people still
call nitrates and nitrites by the older names.

Heating the carbonates


Most carbonates tend to decompose on heating to give the metal oxide and carbon dioxde.
For example, a typical Group 2 carbonate like calcium carbonate decomposes like this:

In Group 1, lithium carbonate behaves in the same way - producing lithium oxide and
carbon dioxide.

The rest of the Group 1 carbonates don't decompose at Bunsen temperatures, although at
higher temperatures they will. The decomposition temperatures again increase as you go
down the Group.

Note: I have severe problems with this - and what I


have said is in line with what UK examiners are likely to
expect, but whether it is the truth, I don't know!
Various data sources give a decomposition
temperature for lithium carbonate as 1310C - well
above Bunsen temperatures (about 1000C maximum
if something is heated directly with no glass getting in
the way). Heslop and Robinson's Inorganic Chemistry
(my copy published in 1960) says that it will
decompose on heating in a stream of hydrogen at
800C. I'm not sure what the purpose of the hydrogen
is. If it was simply to sweep away the carbon dioxide to
prevent it recombining with the oxide, it seems an
unnecessarily hazardous way of doing it!
(January 2012: I have been told by someone working in
the field that in his personal experience, lithium
carbonate decomposes at a temperature of about
790C in a stream of pure nitrogen or dry air. So
perhaps there is nothing special about the hydrogen
mentioned above. The figure given by Heslop and
Robinson is therefore accurate.)
It is also difficult to get reliable results if you heat these
carbonates in the lab. They all tend to react with water
vapour and carbon dioxide in the air to produce
hydrogencarbonates - and these decompose easily on
heating, releasing the carbon dioxide again. Therefore
heating a normal lab sample of, say, sodium carbonate
does often produce some carbon dioxide because of
this contamination. It is difficult to say categorically that
no carbon dioxide is being produced from the sodium
carbonate.

The thermal stability of the hydrogencarbonates


The Group 2 hydrogencarbonates like calcium hydrogencarbonate are so unstable to heat
that they only exist in solution. Any attempt to get them out of solution causes them to
decompose to give the carbonate, carbon dioxide and water.

By contrast, the Group 1 hydrogencarbonates are stable enough to exist as solids,


although they do decompose easily on heating. For example, for sodium
hydrogencarbonate:

Note: There is complete disagreement in various


sources about lithium hydrogencarbonate. Some say it
only exists in solution; some quote it as a solid. The
only reasonably definitive information I managed to
track down was from the Handbook of Inorganic
Compounds edited by Perry and Phillips. This quotes a
colour for lithium hydrogencarbonate as "white", and a
solubility in water of 5.5g per 100 ml at 13C. Both of
these statements imply to me that it is a solid.

Explanations for the trends in thermal stability


Detailed explanations are given for the carbonates because the diagrams are easier to
draw. Exactly the same arguments apply to the nitrates or hydrogencarbonates.
There are two ways of explaining the increase in thermal stability as you go down the
Group. The hard way is in terms of the energetics of the process; the simple way is to look
at the polarising ability of the positive ions.
Note: The UK A level syllabuses which talk about
Group 1 chemistry only want the simpler way. If you are
interested in the energetics arguments, you will find
them discussed at length for Group 2 compounds by
following this link. Be prepared for some seriously hard
work!
The explanation below on the polarising ability of the
positive ions is taken from that page with only minor
modifications.

Explaining the trend in terms of the polarising ability of the positive ion
A small positive ion has a lot of charge packed into a small volume of space - especially if it
has more than one positive charge. It has a high charge density and will have a marked
distorting effect on any negative ions which happen to be near it.
A bigger positive ion has the same charge spread over a larger volume of space. Its
charge density will be lower, and it will cause less distortion to nearby negative ions.

The structure of the carbonate ion


If you worked out the structure of a carbonate ion using "dots-and-crosses" or some similar
method, you would probably come up with:

This shows two single carbon-oxygen bonds and one double one, with two of the oxygens
each carrying a negative charge. Unfortunately, in real carbonate ions all the bonds are
identical, and the charges are spread out over the whole ion - although concentrated on
the oxygen atoms. We say that the charges aredelocalised.
This is a rather more complicated version of the bonding you might have come across in
benzene or in ions like ethanoate. For the purposes of this topic, you don't need to
understand how this bonding has come about.
Note: If you are interested, you could follow these links
tobenzene or to organic acids. Either of these links is
likely to involve you in a fairly time-consuming detour!

The next diagram shows the delocalised electrons. The shading is intended to show that

there is a greater chance of finding them around the oxygen atoms than near the carbon.

Polarising the carbonate ion


Now imagine what happens when this ion is placed next to a positive ion. The positive ion
attracts the delocalised electrons in the carbonate ion towards itself. The carbonate ion
becomes polarised. The diagram shows what happens with an ion from Group 2, carrying
two positive charges

If this is heated, the carbon dioxide breaks free to leave the metal oxide.
How much you need to heat the carbonate before that happens depends on how polarised
the ion was. If it is highly polarised, you need less heat than if it is only slightly polarised.
If the positive ion only had one positive charge, the polarising effect would be less. That is
why the Group 1 compounds are more thermally stable than those in Group 2. You have to
heat the Group 1 compound more because the carbonate ions are less polarised by singly

charged positive ions.


The smaller the positive ion is, the higher the charge density, and the greater effect it will
have on the carbonate ion. As the positive ions get bigger as you go down the Group, they
have less effect on the carbonate ions near them. To compensate for that, you have to heat
the compound more in order to persuade the carbon dioxide to break free and leave the
metal oxide.
In other words, as you go down the Group, the carbonates become more thermally stable.

What about the nitrates and hydrogencarbonates?


The argument is exactly the same here. The small positive ions at the top of the Group
polarise the nitrate or hydrogencarbonate ions more than the larger positive ions at the
bottom.
And, again, the Group 1 compounds will need to be heated more strongly than those in
Group 2 because the Group 1 ions are less polarising.
Note: The reason for drawing the diagrams for a 2+
ion polarising a carbonate ion is that they are much
easier than any other combination. For everything else
you have more complicated interactions involving more
than one positive or negative ion. The principle is the
same - it's just a lot more difficult to make it easy to
understand because the diagrams would be so
confusing.
Don't worry about this. For UK A level purposes all you
would need to do is talk about how the polarising ability
of the positive ion increases as it gets smaller or more
charged. The diagrams and lengthy explanation above
are just to help you to understand what that means.

The solubility of Group 1 compounds


The facts
For UK A level purposes, the important thing to remember is that Group 1 compounds tend
to be more soluble than the corresponding ones in Group 2.

The carbonates
For example, Group 2 carbonates are virtually insoluble in water. Magnesium carbonate
(the most soluble one I have data for) is soluble to the extent of about 0.02 g per 100 g of
water at room temperature.
By contrast, the least soluble Group 1 carbonate is lithium carbonate. A saturated solution
of it has a concentration of about 1.3 g per 100 g of water at 20C. The other carbonates in
the Group all count as very soluble - increasing to an astonishing 261.5 g per 100 g of
water at this temperature for caesium carbonate.
Solubility of the carbonates increases as you go down Group 1.

The hydroxides
The least soluble hydroxide in Group 1 is lithium hydroxide - but it is still possible to make
a solution with a concentration of 12.8 g per 100 g of water at 20C. The other hydroxides
in the Group are even more soluble.
Solubility of the hydroxides increases as you go down Group 1.
In Group 2, the most soluble one is barium hydroxide - and it is only possible to make a
solution of concentration around 3.9 g per 100 g of water at the same temperature.

I'm not even going to attempt an explanation of these trends!

Trying to explain trends in solubility is a complete nightmare. If you have read the section
on Group 2 of the Periodic Table, you may know that I have shown why the usual
explanations given for these trends at this level don't work.
Note: If you are an absolute glutton for punishment,
you can read about this by following this link to the
page about why the normal explanations for Group 2
solubility trends don't work! Don't waste time doing this
unless you know about entropy.

Explaining the trends in Group 2 was difficult enough. Comparing them with Group 1 is
going to be even more difficult - particularly in the case of the carbonates, because the
trends in the two Groups are in opposite directions. The carbonates get more soluble as
you go down Group 1, but tend to get less soluble down Group 2.
This is too difficult to talk about at this level - and I'm not going to do it! You
should not need it for UK A level purposes for Group 1. Just learn that Group 1 compounds
tend to be more soluble than their Group 2 equivalents.

The Group 1 hydrides


Saline (salt-like) hydrides
The hydrides of Group 1 metals are white crystalline solids which contain the metal ions
and hydride ions, H-. They have exactly the same crystal structure as sodium chloride that's why they are called saline or salt-like hydrides.
Because they can react violently with water or moist air, they are normally supplied as
suspensions in mineral oil.
Note: You will find the crystal structure of sodium
chloride if you follow this link.
Use the BACK button on your browser to return to this

page.

Preparation of the Group 1 hydrides


These are made by passing hydrogen gas over the heated metal. For example, for lithium
hydride:

Reactions of the Group 1 hydrides


These are limited to the two reactions most likely to be wanted by UK A level syllabuses.
Electrolysis
On heating, most of these hydrides decompose back into the metal and hydrogen before
they melt. It is, however, possible to melt lithium hydride and to electrolyse the melt.
The metal is released at the cathode as you would expect. Hydrogen is given off at the
anode (the positive electrode) and this is evidence for the presence of the negative hydride
ion in lithium hydride.
The anode equation is:

The other Group 1 hydrides can be electrolysed in solution in various molten mixtures such
as a mixture of lithium chloride and potassium chloride. Mixtures such as these melt at
lower temperatures than the pure chlorides.

Reaction with water


These hydrides react violently with water releasing hydrogen gas and producing the metal

hydroxide.
For example, sodium hydride reacts with water to produce a solution of sodium hydroxide
and hydrogen gas.

FLAME TESTS

This page describes how to do a flame test for a range of metal ions, and briefly
describes how the flame colour arises.
Flame tests are used to identify the presence of a relatively small number of metal
ions in a compound. Not all metal ions give flame colours.
For Group 1 compounds, flame tests are usually by far the easiest way of identifying
which metal you have got. For other metals, there are usually other easy methods
which are more reliable - but the flame test can give a useful hint as to where to
look.

Carrying out a flame test


Practical details
Clean a platinum or nichrome (a nickel-chromium alloy) wire by dipping it into
concentrated hydrochloric acid and then holding it in a hot Bunsen flame. Repeat
this until the wire doesn't produce any colour in the flame.
Note: There will, in fact, always
be a trace of orange in the flame
if you use nichrome. You soon

learn to ignore this. Platinum is


much better to use, but is much,
much more expensive. If you
have a particularly dirty bit of
nichrome wire, you can just chop
the end off. You don't do that
with platinum!
Dilute hydrochloric acid can be
used instead of concentrated
acid for safety reasons, but
doesn't always give such intense
flame colours.

When the wire is clean, moisten it again with some of the acid and then dip it into a small
amount of the solid you are testing so that some sticks to the wire. Place the wire back in
the flame again.
If the flame colour is weak, it is often worthwhile to dip the wire back in the acid again and
put it back into the flame as if you were cleaning it. You often get a very short but intense
flash of colour by doing that.

The colours
The colours in the table are just a guide. Almost everybody sees and describes colours
differently. I have, for example, used the word "red" several times to describe colours which
can be quite different from each other. Other people use words like "carmine" or "crimson"
or "scarlet", but not everyone knows the differences between these words - particularly if
their first language isn't English.

flame colour
Li

red

Na
K

strong persistent orange


lilac (pink)

Rb

red (reddish-violet)

Cs

blue-violet (see below)

Ca

orange-red

Sr

red

Ba

pale green

Cu

blue-green (often with white flashes)

Pb

greyish-white

What do you do if you have a red flame colour for an unknown compound and don't know
which of the various reds it is?
Get samples of known lithium, strontium (etc) compounds and repeat the flame test,
comparing the colours produced by one of the known compounds and the unknown
compound side by side until you have a good match.
Note: There is a lot of
disagreement on the web and in
the books I have looked at about
the flame colour given by
caesium compounds, and I have
never actually done this myself
in the lab. However, I have
received a helpful email from a
student who says: "At my school
we did some flame testing
experiments, and . . . caesium is
actually either blue or violet,

depending on the way you look


at it. I think it looks more violet
than blue, but it sort of changes
each time you do it." (Kara
Gates, March 2006). If you
thought chemistry was clear-cut,
you are sadly mistaken!
Since then (February 2015) I
came across a video on
YouTube from the Royal Society
of Chemistry showing the colour
clearly. The flame in this video
was produced by burning
methanol contaminated with a
caesium compound. I'm not sure
why there is some orange in
some parts of the flame curiously, it is quite localised.
Don't count that as a part of the
caesium flame colour!

The origin of flame colours


Flame colours are produced from the movement of the electrons in the metal ions present
in the compounds.
For example, a sodium ion in an unexcited state has the structure 1s 22s22p6.
When you heat it, the electrons gain energy and can jump into any of the empty orbitals at
higher levels - for example, into the 7s or 6p or 4d or whatever, depending on how much
energy a particular electron happens to absorb from the flame.
Because the electrons are now at a higher and more energetically unstable level, they tend
to fall back down to where they were before - but not necessarily all in one go.
An electron which had been excited from the 2p level to an orbital in the 7 level, for
example, might jump back to the 2p level in one go. That would release a certain amount

of energy which would be seen as light of a particular colour.


However, it might jump back in two (or more) stages. For example, first to the 5 level and
then back to the 2 level.
Each of these jumps involves a specific amount of energy being released as light energy,
and each corresponds to a particular colour.
As a result of all these jumps, a spectrum of coloured lines will be produced. The colour
you see will be a combination of all these individual colours.
The exact sizes of the possible jumps in energy terms vary from one metal ion to another.
That means that each different ion will have a different pattern of spectral lines, and so a
different flame colour.

ATOMIC AND PHYSICAL PROPERTIES OF THE GROUP 2 ELEMENTS

This page explores the trends in some atomic and physical properties of
the Group 2 elements - beryllium, magnesium, calcium, strontium and
barium. You will find separate sections below covering the trends in atomic
radius, first ionisation energy, electronegativity and physical properties.
Even if you aren't currently interested in all these things, it would probably
pay you to read most of this page. The same ideas tend to recur
throughout the atomic properties, and you may find that earlier
explanations help to you understand later ones. The physical properties
are extremely difficult to explain, however, and you might not want to read
about those unless you have to.

Trends in Atomic Radius

Note: You will find atomic


radius covered in detail in another part of
this site. If you choose to follow this link,
use the BACK button on your browser to
return quickly to this page.

You can see that the atomic radius increases as you go down the Group. Notice that
beryllium has a particularly small atom compared with the rest of the Group.
Explaining the increase in atomic radius
The radius of an atom is governed by

the number of layers of electrons around the nucleus

the pull the outer electrons feel from the nucleus.

Compare beryllium and magnesium:


Be

1s22s2

Mg

1s22s22p63s2
Note: If you aren't sure about
writing electronic structures using s and
p notation it might be a good idea to
follow this link before you go on. Use the
BACK button on your browser to return

quickly to this page.

In each case, the two outer electrons feel a net pull of 2+ from the nucleus. The positive
charge on the nucleus is cut down by the negativeness of the inner electrons.

This is equally true for all the other atoms in Group 2. Work it out for calcium if you aren't
convinced.
The only factor which is going to affect the size of the atom is therefore the number of
layers of inner electrons which have to be fitted in around the atom. Obviously, the more
layers of electrons you have, the more space they will take up - electrons repel each other.
That means that the atoms are bound to get bigger as you go down the Group.
Note: You may think that this is all a bit
long-winded! It is, after all, fairly obvious
that atoms will get bigger if you add
more layers of electrons. Why, then,
bother about exploring the net pull on the
electrons from the centre of the atom?
It is a matter of setting up good habits. If
you are talking about atoms in the same
Group, the net pull from the centre will
always be the same - and you could
ignore it without creating problems. That
isn't true if you try to compare atoms
from different parts of the Periodic Table.
If you don't get into the habit of thinking

about all the possible factors, you are


going to make mistakes.

Trends in First Ionisation Energy


First ionisation energy is the energy needed to remove the most loosely held electron from
each of one mole of gaseous atoms to make one mole of singly charged gaseous ions - in
other words, for 1 mole of this process:

Note: You will find ionisation


energy covered in detail in another part
of this site. If you choose to follow this
link, use the BACK button on your
browser to return quickly to this page.

Notice that first ionisation energy falls as you go down the group.
Explaining the decrease in first ionisation energy

Ionisation energy is governed by

the charge on the nucleus,

the amount of screening by the inner electrons,

the distance between the outer electrons and the nucleus.

As you go down the Group, the increase in nuclear charge is exactly offset by the increase
in the number of inner electrons. Just as when we were talking about atomic radius further
up this page, in each of the elements in this Group, the outer electrons feel a net attraction
of 2+ from the centre.
However, as you go down the Group, the distance between the nucleus and the outer
electrons increases and so they become easier to remove - the ionisation energy falls.

Trends in Electronegativity
Electronegativity is a measure of the tendency of an atom to attract a bonding pair of
electrons. It is usually measured on the Pauling scale, on which the most electronegative
element (fluorine) is given an electronegativity of 4.0.
Note: You will
find electronegativity covered in detail in
another part of this site. If you choose to
follow this link, use the BACK button on
your browser to return quickly to this
page.

All of these elements have a low electronegativity. (Remember that the most
electronegative element, fluorine, has an electronegativity of 4.0.) Notice that
electronegativity falls as you go down the Group. The atoms become less and less good at
attracting bonding pairs of electrons.
Note: You might argue that the fall
doesn't apply throughout the Group
because both calcium and strontium
appear to have an electronegativity of
1.0. This is probably most easily
explained by the fact that
electronegativities are often only
recorded to 1 decimal place. To two
decimal places, calcium is 1.00 and
strontium is 0.95. When these numbers
are rounded to 1 decimal place, both
would appear to have an
electronegativity of 1.0.

Explaining the decrease in electronegativity


Imagine a bond between a magnesium atom and a chlorine atom. Think of it to start with
as a covalent bond - a pair of shared electrons. The electron pair will be dragged towards
the chlorine end because there is a much greater net pull from the chlorine nucleus than

from the magnesium one.

The electron pair ends up so close to the chlorine that there is essentially a transfer of an
electron to the chlorine - ions are formed.
The large pull from the chlorine nucleus is why chlorine is much more electronegative than
magnesium is.
Now compare this with the beryllium-chlorine bond.
The net pull from each end of the bond is the same as before, but you have to remember
that the beryllium atom is smaller than a magnesium atom. That means that the electron
pair is going to be closer to the net 2+ charge from the beryllium end, and so more strongly
attracted to it.

In this case, the electron pair doesn't get attracted close enough to the chlorine for an ionic
bond to be formed. Because of its small size, beryllium forms covalent bonds, not ionic
ones. The attraction between the beryllium nucleus and a bonding pair is always too great

for ions to be formed.


Summarising the trend down the Group
As the metal atoms get bigger, any bonding pair gets further and further away from the
metal nucleus, and so is less strongly attracted towards it. In other words, as you go down
the Group, the elements become less electronegative.
As you go down the Group, the bonds formed between these elements and other things
such as chlorine become more and more ionic. The bonding pair is increasingly attracted
away from the Group 2 element towards the chlorine (or whatever).

Trends in Melting Point, Boiling Point, and Atomisation Energy


The facts
Melting points

You will see that (apart from where the smooth trend is broken by magnesium) the melting
point falls as you go down the Group.
Boiling points

You will see that there is no obvious pattern in boiling points. It would be quite wrong to
suggest that there is any trend here whatsoever.
Atomisation energy
This is the energy needed to produce 1 mole of separated atoms in the gas state starting
from the element in its standard state (the state you would expect it to be in at
approximately room temperature and pressure).

And again there is no simple pattern. It looks similar to, but notexactly the same as, the
boiling point chart.
Warning! Unless you are doing a
syllabus which expects you to be able to

explain this, or unless your chemistry is


good and you like a good argument,
don't read on beyond this point.

Trying to explain this


The only explanations you are likely to ever come across relate to the melting points. I will
give you the most common explanation, and then explain why I think it is completely wrong!
The faulty explanation
All of these elements are held together by metallic bonds. The melting points get lower as
you go down the Group because the metallic bonds get weaker. The oddity of magnesium
has to be explained separately.
The atoms in a metal are held together by the attraction of the nuclei to the delocalised
electrons. As the atoms get bigger, the nuclei get further away from these delocalised
electrons, and so the attractions fall. That means that the atoms are more easily separated
to make a liquid and finally a gas.
As you go down the Group, the arrangement of the atoms in the various solid metals
changes. Beryllium and magnesium are both hexagonal close-packed; calcium and
strontium are face-centred cubic; barium is body-centred cubic. Don't worry if you don't
know what this means. All that matters is that there is a change in crystal structure
between magnesium and calcium. That is supposed to account for the fact that magnesium
is out of line with the rest of the Group.

Why I don't believe this explanation


The odd position of magnesium
Let's take this first, because that argument is relatively easy to demolish.
Despite the fact that the first four elements have two different structures, those structures
are both 12-co-ordinated. Each atom is touched by 12 surrounding atoms. In that case, you
would expect the metallic bond to be similar in each case, because the orbitals are going to

overlap and delocalise in the same sort of way. Any differences just due to the structures
should only be minor.
By contrast, barium is 8-co-ordinated (like the Group 1 metals). That's a less efficient
packing, and you might expect that to be reflected in a much weaker metallic bond.
Although the barium melting point is lower than that of strontium, it isn't dramatically lower.
It just follows the general trend - suggesting that the major change of structure isn't making
much difference. You can't have it both ways! If a minor change of structure at magnesiumcalcium makes a huge difference, then a major one at barium should make an even bigger
difference. It obviously doesn't.
The strength of the metallic bonds
Melting point isn't a good guide to the strength of the metallic bonds. When a metal melts,
the bonds aren't completely broken - only loosened enough for the atoms to move around.
Metallic bonds are still present in the molten metal, and aren't entirely broken until it boils.
That means that boiling point, or the size of the atomisation energy, is a much better guide
to the real strengths of the metallic bonds. With both of those measures, you are ending up
with free atoms in the gas state with the metallic bond completely broken.
Cotton and Wilkinson, in their classic degree level bookAdvanced Inorganic Chemistry say
"The strength of binding between the atoms in metals can conveniently be measured by
the energies of atomization of the metallic elements." (Third edition, page 68.)
If you look back at the atomisation energy chart above, you will see that magnesium still
has the lowest value, but there is no obvious trend in atomisation energies as you go down
the Group. The explanation about weaker metallic bonds as you go down the Group can't
be accurate either.
If you look at figures for Group 1 rather than Group 2, then the trends for all the various
measures (melting point, boiling point and atomisation energy) work almost perfectly as
you go down the Group. There is obviously something happening in Group 2 which is
causing the problem. I have no idea at all what it might be.

A final comment
I have had a request for solid information about this on Chemguide since 2002, during
which time this page will have been read by hundreds of thousands, if not millions, of
visitors. In all that time, nobody has suggested an explanation which would account for the
low melting point value for magnesium, or the lack of any pattern with the other two
properties.
If you can see flaws in what I have said above, please get in touch with me. I would also be
grateful to anyone who could point me towards an explanation, even if it is too difficult to
use at this level, or even too difficult for me to understand. But that explanation has to be
capable of accounting for all the variations in the data.
There is one book that I have come across which is honest enough to admit the difficulty.
A.G.Sharpe, in his degree level book Inorganic Chemistry admits that there is no easy
explanation for the variations in the physical data in Group 2. If that is indeed the case, as
looks pretty likely, it is a pity that anyone should encourage faulty explanations like the one
above. Much better to have no explanation than a deeply flawed one.
REACTIONS OF THE GROUP 2 ELEMENTS WITH WATER
This page looks at the reactions of the Group 2 elements - beryllium, magnesium,
calcium, strontium and barium - with water (or steam). It uses these reactions
to explore the trend in reactivity in Group 2.
The Facts
Beryllium
Beryllium has no reaction with water or steam even at red heat.
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).
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. (This is just like the aluminium case that you are probably familiar with.) If you
add that to the trends explained below, beryllium turns out to be very unreactive.

Looking at the enthalpy changes for the reactions

The enthalpy change of a reaction is a measure of the amount of heat absorbed or evolved
when the reaction takes place. An enthalpy change is negative if heat is evolved, and
positive if it is absorbed. That's really all you need to know for this section!
Note: If you aren't happy about enthalpy changes, you might want to explore
the energetics section of Chemguide, or my chemistry calculations book.

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, only the magnesium reaction actually happens. The
explanation for the different reactivities must lie somewhere else.
Similarly, if you calculate the enthalpy changes for the reactions between calcium,
strontium or barium and cold water, you again find that the amount of heat evolved in each
case is almost exactly the same - in this case, about -430 kJ mol -1.
The reason for the increase in reactivity must again lie elsewhere.

Looking at the activation energies for the reactions


The activation energy for a reaction is the minimum amount of energy which is needed in
order for the reaction to take place. It doesn't matter how exothermic the reaction would be
once it got started - if there is a high activation energy barrier, the reaction will take place
very slowly, if at all.
When Group 2 metals react to form oxides or hydroxides, metal ions are formed.
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.

Note: If you are unhappy about the changes in ionisation energy as you go
down Group 2 you should follow this link. You will find a further link to a wider
discussion of ionisation energy if you need it.

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.

EACTIONS OF THE GROUP 2 ELEMENTS WITH AIR OR OXYGEN

This page looks at the reactions of the Group 2 elements - beryllium, magnesium,
calcium, strontium and barium - with air or oxygen. It explains why it is difficult to
observe many tidy patterns.

The Facts
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 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.
To be able to make any sensible comparison, you would have to have pieces of
metal which were all equally free of oxide coating, with exactly the same surface
area and shape, exactly the same flow of oxygen around them, and heated to exactly
the same extent to get them started. It can't be done!
Note: One of the UK Exam Boards (OCR)
implies in their syllabus that you should be
able to state a trend and then explain it in
terms of ionisation energy differences.
You cando this with the reactions with
water (or steam), and you might like to
follow this link if you haven't already been
there. Trying to account for a non-existent
trend in the reactions with oxygen is just
silly!

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.
You can find them at
video 1
video 2
video 3
You might possibly be able to imagine a
trace of very pale greenish colour
surrounding the white flame in the third
video, but to my eye, they all count as a
white flame. Anything else that I could find
in a short clip from YouTube involved a
flame test for a barium compound,
irrespective of how it was described in the
video.
Barium does not burn with a green flame!

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 reactions with air


The reactions of the Group 2 metals with air rather than oxygen is complicated by the fact
that they all react with nitrogen to produce nitrides. In each case, you will get a mixture of
the metal oxide and the metal nitride.
The general equation for the Group is:

The familiar white ash you get when you burn magnesium ribbon in air is a mixture of
magnesium oxide and magnesium nitride (despite what you might have been told when
you were first learning Chemistry!).

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:

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.
Note: This has been argued through in
detail on the page about the reactions of
these metals with water (or steam). If you
need to know about the reactions with
oxygen, you will almost certainly need to
know about the reactions with water as
well.

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 avery 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.

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.

Why do these metals form nitrides on heating in air?


Nitrogen is often thought of as being fairly unreactive, and yet all these metals combine
with it to produce nitrides, X3N2, containing X2+ and N3- ions.
Nitrogen is fairly unreactive because of the very large amount of energy needed to break

the triple bond joining the two atoms in the nitrogen molecule, N 2.
When something like magnesium nitride forms, you have to supply all the energy needed
to form the magnesium ions as well as breaking the nitrogen-nitrogen bonds and then
forming N3- ions. All of these processes absorb energy.
This energy has to be recovered from somewhere to give an overall exothermic reaction - if
the energy can't be recovered, the overall change will be endothermic and won't happen.
Note: This is a bit of a simplification! In
order to find out whether a reaction is
feasible, you have to consider free energy
changes and not just whether the reaction
is exothermic or endothermic. If you don't
know anything about free energy changes,
don't worry about it. The simplification is
valid in this particular case.

Energy is evolved when the ions come together to produce the crystal lattice. This energy
is known as lattice energy or lattice enthalpy.
The size of the lattice energy depends on the attractions between the ions. The lattice
energy is greatest if the ions are small and highly charged - the ions will be close together
with very strong attractions. In the whole of Group 2, the attractions between the 2+ metal
ions and the 3- nitride ions are big enough to produce very high lattice energies.
When the crystal lattices form, so much energy is released that it more than compensates
for the energy needed to produce the various ions in the first place. The excess energy
evolved makes the overall process exothermic.
This is in contrast to what happens in Group 1 of the Periodic Table (lithium, sodium,
potassium, rubidium and caesium). Their ions only carry one positive charge, and so the
lattice energies of their nitrides will be much less.
Lithium is the only metal in Group 1 to form a nitride. Lithium has by far the smallest ion in
the Group, and so lithium nitride has the largest lattice energy of any possible Group 1
nitride. Only in lithium's case is enough energy released to compensate for the energy

needed to ionise the metal and the nitrogen - and so produce an exothermic reaction
overall.
In all the other cases in Group 1, the overall reaction would be endothermic. Those
reactions don't happen, and the nitrides of sodium and the rest aren't formed.

REACTIONS OF THE GROUP 2 ELEMENTS WITH COMMON ACIDS

This page looks at the reactions of the Group 2 elements - beryllium, magnesium, calcium,
strontium and barium - with common acids.

Reactions with dilute hydrochloric acid


All the metals react with dilute hydrochloric acid to give bubbles of hydrogen and a
colourless solution of the metal chloride.

As you might expect for elements in this part of the Periodic Table, the reactions get more
vigorous as you go down the Group.

Reactions with dilute sulphuric acid


These are more complicated, because of the formation of insoluble sulphates.
Beryllium and magnesium
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 doing chemistry. Bubbles of hydrogen are formed, together with colourless
solutions of beryllium or magnesium sulphate.
For example:

Calcium, strontium and barium


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.
Note: With strontium and barium, I have
never actually seen either reaction, nor can I
find any video clips on the web. I would
expect the reactions to never really get going,
leaving the metal coated with a white solid. If
you have any direct knowledge of this,
preferably with a bit of video to support it,
could you let me know via the address on
the about this sitepage.

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.
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.
Beryllium
There is a lot of disagreement amongst various sources about whether or not beryllium
reacts with nitric acid. Beryllium has a strong oxide layer (rather like the more familiar
aluminium) which slows reactions down until it has been removed.
Some sources say that beryllium doesn't react with nitric acid. On the other hand, it is easy
to find practical details for making beryllium nitrate by reacting beryllium powder with nitric
acid. One source uses semi-concentrated nitric acid, and says that the gas evolved is
nitrogen monoxide. That is what you would expect.
What seems to be happening is that whether it reacts or not depends on the source of the
beryllium (how it was manufactured) - perhaps changing small amounts of impurities in the
metal which affect the reaction.
This is all so uncertain that it seems hard to see how a question could be asked about it in
an exam.
The other Group 2 metals
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:

OLUBILITY OF THE HYDROXIDES, SULPHATES AND CARBONATES OF THE GROUP 2 ELEMENTS IN


WATER
This page looks at the solubility in water of the hydroxides, sulphates and
carbonates of the Group 2 elements - beryllium, magnesium, calcium, strontium
and barium. Although it describes the trends, there isn't any attempt to explain
them on this page - for reasons discussed later.
You will find that there aren't any figures given for any of the solubilities.
There are major discrepancies between the figures given by two common UK A level
Data Books (Nuffield Advanced Science Book of Data, and Chemistry Data Book by
Stark and Wallace). There are also important inconsistencies within the books
(one set of figures doesn't agree with those which can be calculated from
another set). I haven't been able to find data which I am sure is correct, and
therefore prefer not to give any.
The Facts
Solubility of the hydroxides

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

This is a trend which holds for the whole Group, and applies whichever set of
data you choose.
Some examples may help you to remember the trend:
Magnesium hydroxide appears to be insoluble in water. However, if you shake it
with water, filter it and test the pH of the solution, you find that it is
slightly alkaline. This shows that there are more hydroxide ions in the solution
than there were in the original water. Some magnesium hydroxide must have
dissolved.
Calcium hydroxide solution is used as "lime water". 1 litre of pure water will
dissolve about 1 gram of calcium hydroxide at room temperature.
Barium hydroxide is soluble enough to be able to produce a solution with a
concentration of around 0.1 mol dm-3 at room temperature.
Solubility of the sulphates

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

The simple trend is true provided you include hydrated beryllium sulphate in it,
but not if the beryllium sulphate is anhydrous.
The Nuffield Data Book quotes anyhydrous beryllium sulphate, BeSO4,
as insoluble (I haven't been able to confirm this from any other source),
whereas the hydrated form, BeSO4.4H2O is soluble. (The Data Books agree on this
- giving a figure of about 39 g dissolving in 100 g of water at room
temperature.)
Figures for magnesium sulphate and calcium sulphate also vary depending on

whether the salt is hydrated or not, but nothing like so dramatically.


Two common examples may help you to remember the trend:
You are probably familiar with the reaction between magnesium and dilute
sulphuric acid to give lots of hydrogen and a colourless solution of magnesium
sulphate. Notice that you get a solution, not a precipitate. The magnesium
sulphate is obviously soluble.
You may also remember that barium sulphate is formed as a white precipitate
during the test for sulphate ions in solution. The ready formation of a
precipitate shows that the barium sulphate must be pretty insoluble. In fact, 1
litre of water will only dissolve about 2 mg of barium sulphate at room
temperature.
Solubility of the carbonates

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

None of the carbonates is anything more than very sparingly soluble. Magnesium
carbonate (the most soluble one I have data for) is soluble to the extent of
about 0.02 g per 100 g of water at room temperature.
I can't find any data for beryllium carbonate, but it tends to react with water
and so that might confuse the trend.
The trend to lower solubility is, however, broken at the bottom of the Group.
Barium carbonate is slightly more soluble than strontium carbonate.
There are no simple examples which might help you to remember the carbonate
trend.
What - no explanations?
Before I started to write this page, I thought I understood the trends in
solubility patterns including the explanations for them. The more I have dug
around to try to find reliable data, and the more time I have spent thinking
about it, the less I'm sure that it is possible to come up with
any simple explanation of the solubility patterns.
Note: If you are interested in the reasons why I
am unwilling to give the usual over-simplified
explanations, I have described some of the
problems as I see them on a separate page.
That page also includes an attempt at a better
explanation. Unless your syllabus specifically
asks for explanations of these trends, you would
be better off ignoring this follow-up page!

THERMAL STABILITY OF THE GROUP 2 CARBONATES


AND NITRATES
This page looks at the effect of heat on the carbonates and nitrates of the Group 2
elements - beryllium, magnesium, calcium, strontium and barium. It describes and explains

how the thermal stability of the compounds changes as you go down the Group.

The Facts
The effect of heat on the Group 2 carbonates
All the carbonates in this Group undergo thermal decomposition to give the metal oxide
and carbon dioxide gas. Thermal decomposition is the term given to splitting up a
compound by heating it.
All of these carbonates are white solids, and the oxides that are produced are also white
solids.
If "X" represents any one of the elements:

As you go down the Group, the carbonates have to be heated more strongly before they
will decompose.

The carbonates become more stable to heat as you go down the Group.

The effect of heat on the Group 2 nitrates


All the nitrates in this Group undergo thermal decomposition to give the metal oxide,
nitrogen dioxide and oxygen.
The nitrates are white solids, and the oxides produced are also white solids. Brown
nitrogen dioxide gas is given off together with oxygen. Magnesium and calcium nitrates
normally have water of crystallisation, and the solid may dissolve in its own water of
crystallisation to make a colourless solution before it starts to decompose.
Again, if "X" represents any one of the elements:

As you go down the Group, the nitrates also have to be heated more strongly before they

will decompose.

The nitrates also become more stable to heat as you go down the Group.

Summary
Both carbonates and nitrates become more thermally stable as you go down the Group.
The ones lower down have to be heated more strongly than those at the top before they
will decompose.

Explanations
This page offers two different ways of looking at the problem. You need to find out which of
these your examiners are likely to expect from you so that you don't get involved in more
difficult things than you actually need. You should look at your syllabus, and past exam
papers - together with their mark schemes
Note: If you are working towards a UK-based
exam (A level or its equivalent) and haven't got
copies of your syllabus and past papers follow this
link to find out how to get hold of them.

Detailed explanations are given for the carbonates because the diagrams are easier to
draw, and their equations are also easier. Exactly the same arguments apply to the
nitrates.

Explaining the trend in terms of the polarising ability of the positive ion
A small 2+ ion has a lot of charge packed into a small volume of space. It has a
high charge density and will have a marked distorting effect on any negative ions which
happen to be near it.
A bigger 2+ ion has the same charge spread over a larger volume of space. Its charge

density will be lower, and it will cause less distortion to nearby negative ions.
The structure of the carbonate ion
If you worked out the structure of a carbonate ion using "dots-and-crosses" or some similar
method, you would probably come up with:

This shows two single carbon-oxygen bonds and one double one, with two of the oxygens
each carrying a negative charge. Unfortunately, in real carbonate ions all the bonds are
identical, and the charges are spread out over the whole ion - although concentrated on
the oxygen atoms. We say that the charges aredelocalised.
This is a rather more complicated version of the bonding you might have come across in
benzene or in ions like ethanoate. For the purposes of this topic, you don't need to
understand how this bonding has come about.
Note: If you are interested, you could follow these
links tobenzene or to organic acids. Either of these
links is likely to involve you in a fairly timeconsuming detour!

The next diagram shows the delocalised electrons. The shading is intended to show that
there is a greater chance of finding them around the oxygen atoms than near the carbon.

Polarising the carbonate ion


Now imagine what happens when this ion is placed next to a positive ion. The positive ion
attracts the delocalised electrons in the carbonate ion towards itself. The carbonate ion
becomes polarised.

If this is heated, the carbon dioxide breaks free to leave the metal oxide.
How much you need to heat the carbonate before that happens depends on how polarised
the ion was. If it is highly polarised, you need less heat than if it is only slightly polarised.
The smaller the positive ion is, the higher the charge density, and the greater effect it will
have on the carbonate ion. As the positive ions get bigger as you go down the Group, they
have less effect on the carbonate ions near them. To compensate for that, you have to heat
the compound more in order to persuade the carbon dioxide to break free and leave the
metal oxide.
In other words, as you go down the Group, the carbonates become more thermally stable.
What about the nitrates?
The argument is exactly the same here. The small positive ions at the top of the Group
polarise the nitrate ions more than the larger positive ions at the bottom. Drawing diagrams
to show this happening is much more difficult because the process has interactions
involving more than one nitrate ion. You wouldn't be expected to attempt to draw this in an
exam.

Explaining the trend in terms of the energetics of the process


Looking at the enthalpy changes
If you calculate the enthalpy changes for the decomposition of the various carbonates, you
find that all the changes are quite strongly endothermic. That implies that the reactions are
likely to have to be heated constantly to make them happen.
Note: If you aren't happy about enthalpy
changes, you might want to explore the energetics
section of Chemguide, or my chemistry
calculations book.

The calculated enthalpy changes (in kJ mol-1) are given in the table. Figures to calculate
the beryllium carbonate value weren't available. Remember that the reaction we are talking
about is:

MgCO3

+117

CaCO3

+178

SrCO3

+235

BaCO3

+267

You can see that the reactions become more endothermic as you go down the Group.
That's entirely what you would expect as the carbonates become more thermally stable.
You have to supply increasing amounts of heat energy to make them decompose.
Explaining the enthalpy changes
Here's where things start to get difficult! If you aren't familiar with Hess's Law cycles (or
with Born-Haber cycles) and with lattice enthalpies (lattice energies), you aren't going to

understand the next bit. Don't waste your time looking at it.
Using an enthalpy cycle
You can dig around to find the underlying causes of the increasingly endothermic changes
as you go down the Group by drawing an enthalpy cycle involving the lattice enthalpies of
the metal carbonates and the metal oxides.
Confusingly, there are two ways of defining lattice enthalpy. In order to make the argument
mathematically simpler, during the rest of this page I am going to use the less common
version (as far as UK A level syllabuses are concerned):
Lattice enthalpy is the heat needed to split one mole of crystal in its standard state into its
separate gaseous ions. For example, for magnesium oxide, it is the heat needed to carry
out 1 mole of this change:

Note: Lattice enthalpy is more usually defined as


the heat evolved when 1 mole of crystal is formed
from its gaseous ions. In that case, the lattice
enthalpy for magnesium oxide would be -3889 kJ
mol-1. The term we are using here should more
accurately be called the "lattice dissociation
enthalpy".

The cycle we are interested in looks like this:

You can apply Hess's Law to this, and find two routes which will have an equal enthalpy
change because they start and end in the same places.

For reasons we will look at shortly, the lattice enthalpies of both the oxides and carbonates
fall as you go down the Group. But they don't fall at the same rate.
The oxide lattice enthalpy falls faster than the carbonate one. If you think carefully about
what happens to the value of the overall enthalpy change of the decomposition reaction,
you will see that it gradually becomes more positive as you go down the Group.

Explaining the relative falls in lattice enthalpy


The size of the lattice enthalpy is governed by several factors, one of which is the distance
between the centres of the positive and negative ions in the lattice. Forces of attraction are
greatest if the distances between the ions are small. If the attractions are large, then a lot
of energy will have to be used to separate the ions - the lattice enthalpy will be large.
The lattice enthalpies of both carbonates and oxides fall as you go down the Group
because the positive ions are getting bigger. The inter-ionic distances are increasing and
so the attractions become weaker.
ionic radius (nm)
Mg2+

0.065

Ca2+

0.099

O2-

0.140

CO32-

The lattice enthalpies fall at different rates because of the different sizes of the two
negative ions - oxide and carbonate. The oxide ion is relatively small for a negative ion
(0.140 nm), whereas the carbonate ion is large (no figure available).
In the oxides, when you go from magnesium oxide to calcium oxide, for example, the interionic distance increases from 0.205 nm (0.140 + 0.065) to 0.239 nm (0.140 + 0.099) - an
increase of about 17%.
In the carbonates, the inter-ionic distance is dominated by the much larger carbonate ion.
Although the inter-ionic distance will increase by the same amount as you go from

magnesium carbonate to calcium carbonate, as a percentage of the total distance the


increase will be much less.
Some made-up figures show this clearly.
I can't find a value for the radius of a carbonate ion, and so can't use real figures. For the
sake of argument, suppose that the carbonate ion radius was 0.3 nm. The inter-ionic
distances in the two cases we are talking about would increase from 0.365 nm to 0.399 nm
- an increase of only about 9%.
The rates at which the two lattice energies fall as you go down the Group depends on the
percentage change as you go from one compound to the next. On that basis, the oxide
lattice enthalpies are bound to fall faster than those of the carbonates.
What about the nitrates?
The nitrate ion is bigger than an oxide ion, and so its radius tends to dominate the interionic distance. The lattice enthalpy of the oxide will again fall faster than the nitrate. if you
constructed a cycle like that further up the page, the same arguments would apply.
SOME BERYLLIUM CHEMISTRY UNTYPICAL OF GROUP 2

This page describes and explains three examples from beryllium chemistry where it
behaves differently from the rest of Group 2. In fact, there are several similarities between
beryllium and aluminium in Group 3. This is known as a diagonal relationshipand is
discussed on the page about electronegativity.

Beryllium chloride is covalent


The facts
Physical properties
Beryllium chloride, BeCl2, melts at 405C and boils at 520C. That compares with 714C

and 1412C for magnesium chloride.


Notice how much dramatically lower the boiling point of beryllium chloride is compared with
magnesium chloride. The much higher boiling point of magnesium chloride is what you
might expect from the strong forces between the positive and negative ions present.
Because its boiling point is much lower, it follows that beryllium chloride can't contain ions it must be covalent. On the other hand, the melting point is quite high for such a small
covalent molecule. There must be something more complicated going on!
Reaction with water
Beryllium chloride reacts vigorously and exothermically with water with the evolution of
acidic, steamy hydrogen chloride gas. This is typical of covalent chlorides.
In the first instance, it reacts to give hydrated beryllium ions, [Be(H2O)4]2+, and chloride
ions.
But the hydrated beryllium ions (called tetraaquaberyllium ions) are quite strongly acidic.
The small beryllium ion at the centre attracts the electrons in the bonds towards itself, and
that makes the hydrogen atoms in the water even more positive than they usually are. If the
solution is hot and concentrated (as it is likely to be if you add water to solid beryllium
chloride - a very exothermic reaction), chloride ions can remove one or more of these
hydrogen ions to produce hydrogen chloride gas.
All the other ionic chlorides in Group 2 dissolve in water without any obvious reaction.
Note: There is actually a very small amount of reaction between
anhydrous magnesium chloride and water, although you wouldn't
notice it. Magnesium chloride isn't quite as purely ionic as we
sometimes pretend!
Follow this link if you are interested in exploring the naming of
complex ions.
. . . or this one for detailed explanations of why complex ions similar
to the beryllium one are acidic.

The structure of beryllium chloride


As a gas . . .
Beryllium chloride, BeCl2, is a linear molecule with all three atoms in a straight line.
Showing only the outer electrons:

Beryllium chloride is known as an electron-deficient compound because it has the two


empty orbitals at the bonding level.
As a solid . . .
If it had this same simple structure as a solid, you would expect the melting point to be
much lower than it actually is. It is a very small molecule, and so the intermolecular
attractions would be expected to be fairly weak.
Note: If you aren't sure about intermolecular forces (Van der
Waals forces) you could follow this link to find out more about them.
Use the BACK button on your browser to return to this page.

In the solid, the BeCl2 molecules polymerise to make long chains. They do this by forming
coordinate bonds (dative covalent bonds) between lone pairs on chlorine atoms and
adjacent beryllium atoms. The diagram shows a simple dimer - the start of the
polymerisation process.

Note: This is exactly the same as the coordinate bonding in


aluminium chloride. If you aren't happy about coordinate (dative
covalent) bonding, it would pay you to look at this page before you
go on.
Use the BACK button on your browser to return to this page.

You can see from the last diagram that the beryllium atoms are still electron deficient. The
process continues. The next diagram shows the coordinate bonds in the conventional way
using arrows. The arrow goes from the atom which is supplying the pair of electrons to the
atom with the empty orbital.

Make sure that you fully understand how this diagram relates to the dimer shown in the
previous diagram.

Why isn't beryllium chloride ionic?

Beryllium has quite a high electronegativity compared with the rest of the Group. That
means that it attracts a bonding pair of electrons towards itself more strongly than
magnesium and the rest do.
In order for an ionic bond to form, the beryllium has to let go of its electrons. It is too
electronegative to do that.
Note: The trends in electronegativity in Group 2 are discussed on
another page. That page looks at the way the electons are
arranged in the beryllium-chlorine bond compared with the
magnesium-chlorine bond.
Use the BACK button on your browser to return to this page - or
come back via the Group 2 menu.

Beryllium forms 4-coordinated complex ions


Some simple background
Although beryllium doesn't normally form simple ions, Be 2+, it does form ions in solution. In
these, the beryllium ion becomes attached to four water molecules to give a complex ion
with the formula [Be(H2O)4]2+.
The ion is said to be 4-coordinated, or to have a coordination number of 4, because
there are four water molecules arranged around the central beryllium.
Many hydrated metal ions are 6-coordinated. For example, magnesium ions in solution
exist as [Mg(H2O)6]2+.
The water molecules in these ions are attached to the central metal ion via coordinate
bonds (dative covalent bonds). One of the lone pairs on each water molecule is used to
form a bond with an empty orbital in the metal ion.
Each time one of these bonds is formed, energy is released, and the ion becomes more
stable. It would seem logical for the metal ion to form as many bonds like this as it possibly

can.
Note: If you aren't happy about coordinate bonding you mustfollow
this link before you go on. You will find the bonding in hydrated
metal ions discussed in some detail on that page.
Use the BACK button on your browser to return to this page.

Why does beryllium only attach four water molecules?


The hydration of beryllium
The problem is that there has to be somewhere that the lone pairs on the water molecules
can attach to. Beryllium has the electronic structure 1s 22s2. It is helpful to draw this as an
"electrons-in-boxes" diagram:

Note: If you aren't happy about orbitals you really ought to follow
this link before you go on. You may want to explore further in that
part of the site as well. Unless you understand exactly what this
electrons-in-boxes diagram is about, you won't be able to make
sense of what is coming up next.

When beryllium forms a 2+ ion it loses the 2 electrons in the 2s orbital. That leaves the 2-

level completely empty.


The 2-level orbitals reorganise themselves (hybridise) to make four equal orbitals, each of
which can accept a lone pair of electrons from a water molecule. In the next diagram the 1s
electrons have been left out. They aren't relevant to the bonding.

Each water molecule, of course, has two lone pairs of electrons. Only one of them is
shown to avoid cluttering the diagram.
Notice that once four water molecules have bonded in this way, there isn't any more space
available at the bonding level. All the empty orbitals from the original beryllium ion are
being used.
The water molecules arrange themselves to get as far apart as possible - which is pointing
towards the corners of a tetrahedron. The ion therefore has a tetrahedral shape.
The hydration of magnesium
You might think that magnesium would behave just the same, but at the 3-level there are
3d orbitals available as well as 3s and 3p.
When the magnesium ion is formed, it leaves empty 3s, 3p and 3d orbitals. When that ion
is hydrated, it uses the 3s orbital, all three of the 3p orbitals and two of the 3d orbitals.
These are reorganised to leave a total of six empty orbitals which are then used for
bonding.

Why does magnesium stop at attaching six waters? Why doesn't it use the remaining 3d
orbitals as well? You can't physically fit more than six water molecules around the
magnesium - they take up too much room.
What about the other ions in Group 2?
As the ions get bigger, there is less tendency for them to form proper coordinate bonds with
water molecules. The ions become so big that they aren't sufficiently attractive to the lone
pairs on the water molecules to form formal bonds - instead the water molecules tend to
cluster more loosely around the positive ions.
Where they do form coordinate bonds with the water, however, they will be 6-coordinated
just like the magnesium.

Beryllium hydroxide is amphoteric


Amphoteric means that it can react with both acids and bases to form salts.
The other Group 2 hydroxides
The other hydroxides of the Group 2 metals are all basic. They react with acids to form
salts. For example:

Calcium hydroxide reacts with dilute hydrochloric acid to give calcium chloride and water.

Beryllium hydroxide
Beryllium hydroxide reacts with acids, forming solutions of beryllium salts. For example:

But it also reacts with bases such as sodium hydroxide solution. Beryllium hydroxide reacts
with the sodium hydroxide to give a colourless solution of sodium tetrahydroxoberyllate.

This contains the complex ion, [Be(OH)4]2-. The name describes this ion. Tetra means
four; hydroxo refers to the OH groups;beryllate shows that the beryllium is present in a
negative ion. The "ate" ending always shows that the ion is negative.
A simple explanation of what is happening
You need to think about where the beryllium hydroxide came from in the first place. It would
probably have been made by adding sodium hydroxide solution to a solution of a beryllium
salt like beryllium sulphate.
Remember that beryllium ions in solution exist as the hydrated ion, [Be(H 2O)4]2+. The
beryllium has such a strongly polarising effect on the water molecules that hydrogen ions
are very easily removed from them.
The sodium hydroxide solution contains hydroxide ions which are powerful bases. If you
add just the right amount of sodium hydroxide solution, you get a precipitate of what is
normally called "beryllium hydroxide" - but which is a shade more complicated than that!

The product (other than water) is a neutral complex, and it is covalently bonded. All that
has happened to the original complex ion is that two hydrogen ions have been removed
from the water molecules.
You get a precipitate of the neutral complex because of the lack of charge on it. There isn't
enough attraction between this neutral complex and water molecules to bring it into
solution.

What happens if you add an acid to this?


The hydrogen ions that were originally removed are simply replaced. The precipitate
dissolves as the original hydrated beryllium ion is re-formed.

What happens if you add a base?


Adding more hydroxide ions to the neutral complex pulls more hydrogen ions off the water
molecules to give the tetrahydroxoberyllate ion:

The beryllium hydroxide dissolves because the neutral complex is converted into an ion
which will be sufficiently attracted to water molecules.
Why doesn't this happen with, for example, calcium hydroxide?
Calcium hydroxide is truly ionic - and contains simple hydroxide ions, OH -. These react with
hydrogen ions from an acid to form water - and so the hydroxide reacts with acids.
However, there isn't any equivalent to the neutral complex. Adding more hydroxide ions
from a base has no effect because they haven't got anything to react with.
Note: This has been simplified to bring it into line with the sort of
treatment you will meet for the acid-base behaviour of transition
metal hydroxides. In particular, the structure of beryllium hydroxide
is probably even more complicated than has been suggested
above!

SOME BERYLLIUM CHEMISTRY UNTYPICAL OF GROUP


2
This page describes and explains three examples from beryllium chemistry where it
behaves differently from the rest of Group 2. In fact, there are several similarities between

beryllium and aluminium in Group 3. This is known as a diagonal relationshipand is


discussed on the page about electronegativity.

Beryllium chloride is covalent


The facts
Physical properties
Beryllium chloride, BeCl2, melts at 405C and boils at 520C. That compares with 714C
and 1412C for magnesium chloride.
Notice how much dramatically lower the boiling point of beryllium chloride is compared with
magnesium chloride. The much higher boiling point of magnesium chloride is what you
might expect from the strong forces between the positive and negative ions present.
Because its boiling point is much lower, it follows that beryllium chloride can't contain ions it must be covalent. On the other hand, the melting point is quite high for such a small
covalent molecule. There must be something more complicated going on!
Reaction with water
Beryllium chloride reacts vigorously and exothermically with water with the evolution of
acidic, steamy hydrogen chloride gas. This is typical of covalent chlorides.
In the first instance, it reacts to give hydrated beryllium ions, [Be(H 2O)4]2+, and chloride
ions.
But the hydrated beryllium ions (called tetraaquaberyllium ions) are quite strongly acidic.
The small beryllium ion at the centre attracts the electrons in the bonds towards itself, and
that makes the hydrogen atoms in the water even more positive than they usually are. If the
solution is hot and concentrated (as it is likely to be if you add water to solid beryllium
chloride - a very exothermic reaction), chloride ions can remove one or more of these
hydrogen ions to produce hydrogen chloride gas.
All the other ionic chlorides in Group 2 dissolve in water without any obvious reaction.

Note: There is actually a very small amount of reaction between


anhydrous magnesium chloride and water, although you wouldn't
notice it. Magnesium chloride isn't quite as purely ionic as we
sometimes pretend!
Follow this link if you are interested in exploring the naming of
complex ions.
. . . or this one for detailed explanations of why complex ions similar
to the beryllium one are acidic.

The structure of beryllium chloride


As a gas . . .
Beryllium chloride, BeCl2, is a linear molecule with all three atoms in a straight line.
Showing only the outer electrons:

Beryllium chloride is known as an electron-deficient compound because it has the two


empty orbitals at the bonding level.
As a solid . . .
If it had this same simple structure as a solid, you would expect the melting point to be
much lower than it actually is. It is a very small molecule, and so the intermolecular
attractions would be expected to be fairly weak.
Note: If you aren't sure about intermolecular forces (Van der

Waals forces) you could follow this link to find out more about them.
Use the BACK button on your browser to return to this page.

In the solid, the BeCl2 molecules polymerise to make long chains. They do this by forming
coordinate bonds (dative covalent bonds) between lone pairs on chlorine atoms and
adjacent beryllium atoms. The diagram shows a simple dimer - the start of the
polymerisation process.

Note: This is exactly the same as the coordinate bonding in


aluminium chloride. If you aren't happy about coordinate (dative
covalent) bonding, it would pay you to look at this page before you
go on.
Use the BACK button on your browser to return to this page.

You can see from the last diagram that the beryllium atoms are still electron deficient. The
process continues. The next diagram shows the coordinate bonds in the conventional way
using arrows. The arrow goes from the atom which is supplying the pair of electrons to the
atom with the empty orbital.

Make sure that you fully understand how this diagram relates to the dimer shown in the
previous diagram.

Why isn't beryllium chloride ionic?


Beryllium has quite a high electronegativity compared with the rest of the Group. That
means that it attracts a bonding pair of electrons towards itself more strongly than
magnesium and the rest do.
In order for an ionic bond to form, the beryllium has to let go of its electrons. It is too
electronegative to do that.
Note: The trends in electronegativity in Group 2 are discussed on
another page. That page looks at the way the electons are
arranged in the beryllium-chlorine bond compared with the
magnesium-chlorine bond.
Use the BACK button on your browser to return to this page - or
come back via the Group 2 menu.

Beryllium forms 4-coordinated complex ions


Some simple background
Although beryllium doesn't normally form simple ions, Be 2+, it does form ions in solution. In
these, the beryllium ion becomes attached to four water molecules to give a complex ion
with the formula [Be(H2O)4]2+.
The ion is said to be 4-coordinated, or to have a coordination number of 4, because

there are four water molecules arranged around the central beryllium.
Many hydrated metal ions are 6-coordinated. For example, magnesium ions in solution
exist as [Mg(H2O)6]2+.
The water molecules in these ions are attached to the central metal ion via coordinate
bonds (dative covalent bonds). One of the lone pairs on each water molecule is used to
form a bond with an empty orbital in the metal ion.
Each time one of these bonds is formed, energy is released, and the ion becomes more
stable. It would seem logical for the metal ion to form as many bonds like this as it possibly
can.
Note: If you aren't happy about coordinate bonding you mustfollow
this link before you go on. You will find the bonding in hydrated
metal ions discussed in some detail on that page.
Use the BACK button on your browser to return to this page.

Why does beryllium only attach four water molecules?


The hydration of beryllium
The problem is that there has to be somewhere that the lone pairs on the water molecules
can attach to. Beryllium has the electronic structure 1s 22s2. It is helpful to draw this as an
"electrons-in-boxes" diagram:

Note: If you aren't happy about orbitals you really ought to follow
this link before you go on. You may want to explore further in that
part of the site as well. Unless you understand exactly what this
electrons-in-boxes diagram is about, you won't be able to make
sense of what is coming up next.

When beryllium forms a 2+ ion it loses the 2 electrons in the 2s orbital. That leaves the 2level completely empty.
The 2-level orbitals reorganise themselves (hybridise) to make four equal orbitals, each of
which can accept a lone pair of electrons from a water molecule. In the next diagram the 1s
electrons have been left out. They aren't relevant to the bonding.

Each water molecule, of course, has two lone pairs of electrons. Only one of them is
shown to avoid cluttering the diagram.
Notice that once four water molecules have bonded in this way, there isn't any more space
available at the bonding level. All the empty orbitals from the original beryllium ion are

being used.
The water molecules arrange themselves to get as far apart as possible - which is pointing
towards the corners of a tetrahedron. The ion therefore has a tetrahedral shape.
The hydration of magnesium
You might think that magnesium would behave just the same, but at the 3-level there are
3d orbitals available as well as 3s and 3p.
When the magnesium ion is formed, it leaves empty 3s, 3p and 3d orbitals. When that ion
is hydrated, it uses the 3s orbital, all three of the 3p orbitals and two of the 3d orbitals.
These are reorganised to leave a total of six empty orbitals which are then used for
bonding.

Why does magnesium stop at attaching six waters? Why doesn't it use the remaining 3d
orbitals as well? You can't physically fit more than six water molecules around the
magnesium - they take up too much room.
What about the other ions in Group 2?
As the ions get bigger, there is less tendency for them to form proper coordinate bonds with
water molecules. The ions become so big that they aren't sufficiently attractive to the lone
pairs on the water molecules to form formal bonds - instead the water molecules tend to
cluster more loosely around the positive ions.
Where they do form coordinate bonds with the water, however, they will be 6-coordinated
just like the magnesium.

Beryllium hydroxide is amphoteric


Amphoteric means that it can react with both acids and bases to form salts.
The other Group 2 hydroxides
The other hydroxides of the Group 2 metals are all basic. They react with acids to form
salts. For example:

Calcium hydroxide reacts with dilute hydrochloric acid to give calcium chloride and water.
Beryllium hydroxide
Beryllium hydroxide reacts with acids, forming solutions of beryllium salts. For example:

But it also reacts with bases such as sodium hydroxide solution. Beryllium hydroxide reacts
with the sodium hydroxide to give a colourless solution of sodium tetrahydroxoberyllate.

This contains the complex ion, [Be(OH)4]2-. The name describes this ion. Tetra means
four; hydroxo refers to the OH groups;beryllate shows that the beryllium is present in a
negative ion. The "ate" ending always shows that the ion is negative.
A simple explanation of what is happening
You need to think about where the beryllium hydroxide came from in the first place. It would
probably have been made by adding sodium hydroxide solution to a solution of a beryllium
salt like beryllium sulphate.
Remember that beryllium ions in solution exist as the hydrated ion, [Be(H 2O)4]2+. The
beryllium has such a strongly polarising effect on the water molecules that hydrogen ions
are very easily removed from them.
The sodium hydroxide solution contains hydroxide ions which are powerful bases. If you
add just the right amount of sodium hydroxide solution, you get a precipitate of what is

normally called "beryllium hydroxide" - but which is a shade more complicated than that!

The product (other than water) is a neutral complex, and it is covalently bonded. All that
has happened to the original complex ion is that two hydrogen ions have been removed
from the water molecules.
You get a precipitate of the neutral complex because of the lack of charge on it. There isn't
enough attraction between this neutral complex and water molecules to bring it into
solution.
What happens if you add an acid to this?
The hydrogen ions that were originally removed are simply replaced. The precipitate
dissolves as the original hydrated beryllium ion is re-formed.

What happens if you add a base?


Adding more hydroxide ions to the neutral complex pulls more hydrogen ions off the water
molecules to give the tetrahydroxoberyllate ion:

The beryllium hydroxide dissolves because the neutral complex is converted into an ion
which will be sufficiently attracted to water molecules.
Why doesn't this happen with, for example, calcium hydroxide?
Calcium hydroxide is truly ionic - and contains simple hydroxide ions, OH -. These react with
hydrogen ions from an acid to form water - and so the hydroxide reacts with acids.
However, there isn't any equivalent to the neutral complex. Adding more hydroxide ions
from a base has no effect because they haven't got anything to react with.
Note: This has been simplified to bring it into line with the sort of
treatment you will meet for the acid-base behaviour of transition

metal hydroxides. In particular, the structure of beryllium hydroxide


is probably even more complicated than has been suggested
above!

THE TREND FROM NON-METAL TO METAL IN THE


GROUP 4 ELEMENTS
This page explores the trend from non-metallic to metallic behaviour in the Group 4
elements - carbon (C), silicon (Si), germanium (Ge), tin (Sn) and lead (Pb). It describes
how this trend is shown in the structures and physical properties of the elements, and
finally makes a not entirely successful attempt to explain the trend.

Structures and Physical Properties


Structures of the elements
The trend from non-metal to metal as you go down the Group is clearly seen in the
structures of the elements themselves.
Carbon at the top of the Group has giant covalent structures in its two most familiar
allotropes - diamond and graphite.
Allotropes: Two or more forms of the same element in
the same physical state.
The structures of diamond and graphite are explored in
more detail on a page about giant covalent structures in
another part of this site. It would probably be worth your
while to read this page before you go any further.
Use the BACK button on your browser to return quickly
to this page.

Diamond has a three-dimensional structure of carbon atoms each joined covalently to 4


other atoms. The diagram shows a small part of that structure.

Exactly this same structure is found in silicon and germanium and in one of the allotropes
of tin - "grey tin" or "alpha-tin".
The common allotrope of tin ("white tin" or "beta-tin") is metallic and has its atoms held
together by metallic bonds. The structure is a distorted close-packed arrangement. In
close-packing, each atom is surrounded by 12 near-neighbours.
By the time you get to lead, the atoms are arranged in a straightforward 12-co-ordinated
metallic structure.
Note: If you aren't sure about metallic
bonding or metallic structures, you should follow these
links before you go any further. The first link will
actually lead you to the second one if you want to
explore both of these topics.
Use the BACK button on your browser to return to this
page.

There is therefore a clear trend from the typical covalency found in non-metals to the
metallic bonding in metals, with the change-over obvious in the two entirely different
structures found in tin.

Physical properties of the elements


Melting points and boiling points
If you look at the trends in melting and boiling points as you go down Group 4, it is very
difficult to make any sensible comments about the shift from covalent to metallic bonding.
The trends reflect the increasing weakness of the covalent or metallic bonds as the atoms
get bigger and the bonds get longer.

The low value for tin's melting point compared with lead is presumably due to tin forming a
distorted 12-co-ordinated structure rather than a pure one. The tin values in the chart refer
to metallic white tin.
Note: The data in this chart comes from the University
of Sheffield's excellent Webelements site. There is an
awful lot of variability in the data depending on where
you get it from. I have to admit to choosing this set
because it shows simple, largely unbroken patterns!

Brittleness
There is a much clearer non-metal / metal difference shown if you look at the brittleness of
the elements.
Carbon as diamond is, of course, very hard - reflecting the strength of the covalent bonds.
However, if you hit it with a hammer, it shatters. Once you apply enough energy to break

the existing carbon-carbon bonds, that's it!


Silicon, germanium and grey tin (all with the same structure as diamond) are also brittle
solids.
However, white tin and lead have metallic structures. The atoms can roll over each other
without any permanent disruption of the metallic bonds - leading to typical metallic
properties like being malleable and ductile. Lead in particular is a fairly soft metal.

Electrical conductivity
Carbon as diamond doesn't conduct electricity. In diamond the electrons are all tightly
bound and not free to move.
Note: In graphite, each atom donates one electron to a
delocalised system of electrons which takes in the
whole of its layer. These electrons are free to move
around, and so graphite conducts electricity - but this is
a special case.
If you are interested, the bonding in graphite is like a
vastly extended version of the bonding in benzene.
Each carbon atom undergoes sp2 hybridisation, and
then the unhybridised p orbitals on each carbon atom
overlap sideways to give a massive pi system above
and below the plane of the sheet of atoms.

Unlike diamond (which doesn't conduct electricity), silicon, germanium and grey tin
are semiconductors.
Semiconductors: The theory of semiconductors lies
outside A level chemistry, but briefly . . .
When lots of atoms come together to make a giant
structure, their atomic orbitals merge to produce a huge

number of molecular orbitals, which arrange


themselves in bands of increasing energy. One of these
is often described as avalence band. The molecular
orbitals in this band hold the electrons which make up
the normal covalent (or metallic) bonding.
The other band is called the conductance band. This
usually has a higher energy than the valence band, and
in something like diamond or silicon at absolute zero,
the conductance band is empty of electrons.
However, as electrons gain thermal energy as the
temperature increases, some electrons may jump from
the valence band into the conductance band especially if the gap between the two is small. Once
they are in the conductance band, they are delocalised
from their original atoms and are free to move and
conduct electricity.
In diamond, the energy gap between the valence band
and conductance band is too high for this to happen. In
silicon, the band gap is small enough for electrons to
jump, and so silicon is a semiconductor.
If you are interested in this, you might like to try a
Google search on silicon semiconductors band
theory (or similar).

White tin and lead are normal metallic conductors of electricity.


There is therefore a clear trend from the typically non-metallic conductivity behaviour of
carbon as diamond, and the typically metallic behaviour of white tin and lead.

Trying to explain the trends


The main characteristic of metals is that they form positive ions. What we need to do is to
look at the factors which increase the likelihood of positive ions being formed as you go

down Group 4.
Electronegativity
Electronegativity is a measure of the tendency of an atom to attract a bonding pair of
electrons. It is usually measured on the Pauling scale, where the most electronegative
element (fluorine) is given an electronegativity of 4.
The lower the electronegativity of an atom, the less strongly the atom attracts a bonding
pair of electrons. That means that this atom will tend to lose the electron pair towards
whatever else it is attached to. The atom we are interested in will therefore tend to carry
either a partial positive charge or form a positive ion.
Metallic behaviour is usually associated with a low electronegativity.
Note: If you aren't sure about electronegativity you
really ought to read about it before you go any further.
Use the BACK button on your browser to return quickly
to this page.

So what happens to electronegativity in Group 4? Does it decrease as you go down the


Group, suggesting a trend towards metallic behaviour?

Well! It certainly falls from carbon to silicon, but from there on it is a complete mess!
There therefore seems to be no relationship between the non-metal to metal trend and the
electronegativity values. Assuming the electronegativity values are correct, I am completely
at a loss to understand this!
Note: The data in this chart again comes from the
University of Sheffield's Webelements site. Again, there
is an awful lot of variability in the data depending on
where you get it from. But in no case that I have found
is there any trend to lower electronegativities as you go
down the Group. Older data sources give a fall from
carbon (2.5) to silicon (1.8), but then give all the other
elements in the Group the same value (all 1.8).
If anyone reading this has a simple explanation for the
lack of correlation between the trend to metallic
behaviour and the electronegativity values, could you
please contact me via the address on the about this
site page.

Ionisation energies
If you are thinking about the formation of positive ions, the obvious place to start looking is
how ionisation energies change as you go down Group 4.
Ionisation energies are defined as the energy needed to carry out each of the following
changes. They are quoted in kJ mol-1.
First ionisation energy:

Second ionisation energy:

. . . and so on.
Note: If you aren't sure about ionisation energies it
would pay you to follow this link before you go any
further.
Use the BACK button on your browser to return quickly
to this page.

None of the Group 4 elements form 1+ ions, so looking at the first ionisation energy alone
isn't very helpful. Some of the elements do, however, form 2+ and (to some extent) 4+ ions.
The first chart shows how the total ionisation energy needed to form the 2+ ions varies as
you go down the Group. The values are all in kJ mol -1.

You can see that the ionisation energies tend to fall as you go down the Group - although
there is a slight increase at lead. The main trend is because:

The atoms are getting bigger because of the extra layers of electrons. The further
the outer electrons are from the nucleus, the less they are attracted - and so the
easier they are to remove.

The outer electrons are screened from the full effect of the nucleus by the increasing
number of inner electrons.

These two effects outweigh the effect of the increasing nuclear charge.

Note: The reason for the oddity at lead is discussed in


some more detail on a page about the oxidation
states shown by elements in Group 4. It isn't
particularly important to the present discussion.

If you look at the amount of ionisation energy needed to form 4+ ions, the pattern is similar,
but not entirely clear cut. Again, the values are all in kJ mol -1.

Note: The increase in total ionisation energy at lead is


even more obvious in the case of the possible
formation of 4+ ions. This is important when it comes to
looking at the preferred oxidation states of lead.

What is clear looking at these two charts is that you have to put in large amounts of
ionisation energy to form 2+ ions, and huge amounts to form 4+ ions.
However, in each case there is a fall in ionisation energy as you go down the Group which
makes it more likely that tin and leadcould form positive ions - however, there is no

indication from these figures that they are likely to form positive ions.
The ionisation energies of carbon at the top of the Group are so huge that there is no
possibility of it forming simple positive ions.
Note: Even for tin and lead, you have to put in huge
amounts of energy to form either 2+ or 4+ ions. So why
do they form ions at all?
You have to remember that there are lots of other
energy terms involved in the formation of an ionic
compound apart from ionisation energy. Some of these
give out large amounts of energy - for example, lattice
enthalpy if you are forming an ionic solid, or hydration
enthalpy if you are forming a solution. You will need to
read about Born-Haber cycles in order to understand
this fully, and you might want to explore the energetics
section of Chemguide, or my chemistry calculations
book.

OXIDATION STATE TRENDS IN GROUP 4


This page explores the oxidation states (oxidation numbers) shown by the Group 4
elements - carbon (C), silicon (Si), germanium (Ge), tin (Sn) and lead (Pb). It looks at the
increasing tendency of the elements to form compounds in which their oxidation states are
+2, particularly with reference to tin and lead.
Note: If you aren't happy about oxidation and
reduction(including the use of oxidation states), it is
essential to follow this link before you go any further.
Use the BACK button on your browser to return quickly
to this page.

Some examples of the trends in oxidation states


The overall trend
The typical oxidation state shown by elements in Group 4 is +4, found in compounds like
CCl4, SiCl4 and SnO2.
Warning: Don't fall into the trap of quoting CH4 as an
example of carbon with a typical oxidation state of +4.
Because carbon is more electronegative than
hydrogen, its oxidation state in this instance is -4!

However, as you go down the Group, there are more and more examples where the
oxidation state is +2, such as SnCl2, PbO, and Pb2+.
With tin, the +4 state is still more stable than the +2, but by the time you get to lead, the +2
state is the more stable - and dominates the chemistry of lead.

An example from carbon chemistry


The only common example of the +2 oxidation state in carbon chemistry occurs in carbon
monoxide, CO. Carbon monoxide is a strong reducing agent because it is easily oxidised to
carbon dioxide - where the oxidation state is the more thermodynamically stable +4.
For example, carbon monoxide reduces many hot metal oxides to the metal - a reaction
which is used, for example, in the extraction of iron in a blast furnace.

Examples from tin chemistry


By the time you get down the Group as far as tin, the +2 state has become increasingly

common, and there is a good range of both tin(II) and tin(IV) compounds. However, tin(IV)
is still the more stable oxidation state of tin.
That means that it will be fairly easy to convert tin(II) compounds into tin(IV) compounds.
This is best shown in the fact that Sn2+ions in solution are good reducing agents.
For example, a solution containing tin(II) ions (for example, tin(II) chloride solution) will
reduce a solution of iodine to iodide ions. In the process, the tin(II) ions are oxidised to
tin(IV) ions.

Note: For simplicity, I am writing this equation (and the


next few) as if the product contained simple tin(IV) ions.
In fact, simple tin(IV) ions don't exist in solution. In
these examples, they will usually be a part of a much
larger complex ion. Don't worry about this at this level.

Tin(II) ions also reduce iron(III) ions to iron(II) ions. For example, tin(II) chloride solution will
reduce iron(III) chloride solution to iron(II) chloride solution. In the process, the tin(II) ions
are oxidised to the more stable tin(IV) ions.

Tin(II) ions will also, of course, be easily oxidised by powerful oxidising agents like acidified
potassium manganate(VII) solution (potassium permanganate solution). This reaction
could be used as a titration to find the concentration of tin(II) ions in a solution.

Note: If you aren't happy about titration calculations


(including those involving potassium manganate(VII) ),
you might be interested in my chemistry calculations
book.

And as a final example . . .


In organic chemistry, tin and concentrated hydrochloric acid are traditionally used to reduce
nitrobenzene to phenylamine (aniline). This reaction involves the tin first being oxidised to
tin(II) ions and then further to the preferred tin(IV) ions.
Note: This reaction is dealt with in some detail in the
organic chemistry section of the site on a page about
the preparation of phenylamine.
Use the BACK button on your browser to return to this
page if you choose to follow this link.

Examples from lead chemistry


With lead, the situation is reversed. This time, the lead(II) oxidation state is the more
stable, and there is a strong tendency for lead(IV) compounds to react to give lead(II)
compounds.
Lead(IV) chloride, for example, decomposes at room temperature to give lead(II) chloride
and chlorine gas:

. . . and lead(IV) oxide decomposes on heating to give lead(II) oxide and oxygen.

Lead(IV) oxide also reacts with concentrated hydrochloric acid, oxidising some of the
chloride ions in the acid to chlorine gas. Once again, the lead is reduced from the +4 to the
more stable +2 state.

Trying to explain the trends in oxidation states


There's nothing surprising about the normal Group oxidation state of +4.
All of the elements in the group have the outer electronic structure ns 2npx1npy1, where n
varies from 2 (for carbon) to 6 (for lead). The oxidation state of +4 is where all these outer
electrons are directly involved in the bonding.
As you get closer to the bottom of the Group, there is an increasing tendency for the s 2 pair
not to be used in the bonding. This is often known as the inert pair effect - and is
dominant in lead chemistry.
However, just giving it a name like "inert pair effect" explains nothing. You need to look at
two different explanations depending on whether you are talking about the formation of
ionic or covalent bonds.
Note: What follows is quite likely to be way beyond

what you need for the purposes of UK A level (or its


equivalent) - and is there mainly for interest. To be sure,
refer to your syllabus and, more importantly, to past
exam papers and mark schemes. If you are working
towards a UK-based exam and haven't got these, follow
this link to the syllabuses page to find out how to get
hold of them.

The inert pair effect in the formation of ionic bonds


If the elements in Group 4 form 2+ ions, they will lose the p electrons, leaving the s 2 pair
unused. For example, to form a lead(II) ion, lead will lose the two 6p electrons, but the 6s
electrons will be left unchanged - an "inert pair".
You would normally expect ionisation energies to fall as you go down a Group as the
electrons get further from the nucleus. That doesn't quite happen in Group 4.
This first chart shows how the total ionisation energy needed to form the 2+ ions varies as
you go down the Group. The values are all in kJ mol -1.

Notice the slight increase between tin and lead.


This means that it is slightly more difficult to remove the p electrons from lead than from tin.
However, if you look at the pattern for the loss of all four electrons, the discrepancy
between tin and lead is much more marked. The relatively large increase between tin and
lead must be because the 6s2 pair is significantly more difficult to remove in lead than the
corresponding 5s2 pair in tin.

Again, the values are all in kJ mol-1, and the two charts are to approximately the same
scale.
The reasons for all this lie in the Theory of Relativity. With the heavier elements like lead,
there is what is known as arelativistic contraction of the electrons which tends to draw
the electrons closer to the nucleus than you would expect. Because they are closer to the
nucleus, they are more difficult to remove. The heavier the element, the greater this effect.
This affects s electrons much more than p electrons.
In the case of lead, the relativistic contraction makes it energetically more difficult to
remove the 6s electrons than you might expect. The energy releasing terms when ions are
formed (like lattice enthalpy or hydration enthalpy) obviously aren't enough to compensate
for this extra energy. That means that it doesn't make energetic sense for lead to form 4+
ions.
Note: If you want to find out more about the relativistic
contraction, try a Google search on relativistic
contraction electrons - but expect to get involved in
some heavy reading!

The inert pair effect in the formation of covalent bonds


You need to think about why carbon normally forms four covalent bonds rather than two.
Using the electrons-in-boxes notation, the outer electronic structure of carbon looks like
this:

There are only two unpaired electrons. Before carbon forms bonds, though, it normally
promotes one of the s electrons to the empty p orbital.

That leaves 4 unpaired electrons which (after hybridisation) can go on to form 4 covalent
bonds.
It is worth supplying the energy to promote the s electron, because the carbon can then
form twice as many covalent bonds. Each covalent bond that forms releases energy, and
this is more than enough to supply the energy needed for the promotion.
One possible explanation for the reluctance of lead to do the same thing lies in falling bond
energies as you go down the Group. Bond energies tend to fall as atoms get bigger and
the bonding pair is further from the two nuclei and better screened from them.
For example, the energy released when two extra Pb-X bonds (where X is H or Cl or

whatever) are formed may no longer be enough to compensate for the extra energy
needed to promote a 6s electron into the empty 6p orbital.
This would would be made worse, of course, if the energy gap between the 6s and 6p
orbitals was increased by the relativistic contraction of the 6s orbital.

THE CHLORIDES OF CARBON, SILICON AND LEAD

This page takes a brief look at the tetrachlorides of carbon, silicon and lead, and
also at lead(II) chloride. It looks at their structures, stability and reactions with water.

Structures
Carbon, silicon and lead tetrachlorides
These all have the formula XCl4.
They are all simple covalent molecules with a typical tetrahedral shape. All of them
are liquids at room temperature. (Although at room temperature, lead(IV) chloride
will tend to decompose to give lead(II) chloride and chlorine gas - see below.)
Lead(II) chloride, PbCl2
Lead(II) chloride is a white solid, melting at 501C. It is very slightly soluble in cold
water, but more soluble in hot water. You can think of lead(II) chloride as being
mainly ionic in character.

Stability

At the top of Group 4, the most stable oxidation state shown by the elements is +4.
This is the oxidation state shown by carbon and silicon in CCl4 and SiCl4. These
therefore have no tendency to split up to give dichlorides.
However, the relative stability of the +4 oxidation state falls as you go down the
Group, and the +2 oxidation state becomes the most stable by the time you get to
lead.
Lead(IV) chloride decomposes at room temperature to give the more stable lead(II)
chloride and chlorine gas.

Note:
This oxidation
state trend in
Group 4 is dealt
with in more
detail on another
page in this
section.
Use the BACK
button on your
browser to return
to this page if
you choose to
follow this link.

Reaction with water (hydrolysis)


Carbon tetrachloride (tetrachloromethane)
Carbon tetrachloride has no reaction with water. If you add it to water, it simply forms a

separate layer underneath the layer of water.


Suppose a water molecule is going to react with the carbon tetrachloride. The reaction
would have to start by the water molecule's oxygen attaching itself to the carbon atom via
the oxygen's lone pair. A chlorine atom would get pushed off the carbon in the process.
There are two problems with this.
First, the chlorines are so bulky and the carbon atom so small, that the oxygen can't easily
get at the carbon atom.

. . . and even if it did, there will be a stage where there is considerable cluttering around
that carbon atom before the chlorine atom breaks away completely. There is going to be a
lot of repulsion between the various lone pairs on all the atoms surrounding the carbon.

That cluttering is going to make this half-way stage (properly called a "transition state")
very unstable. A very unstable transition state means a very high activation energy for the
reaction.
The other problem is that there isn't a convenient empty orbital on the carbon that the
oxygen lone pair can attach to.
If it could attach before the chlorine starts to break away, that would be an advantage.
Forming a bond releases energy, and that energy would therefore be readily available for
breaking a carbon-chlorine bond. But in the case of a carbon atom, that isn't possible.

Silicon tetrachloride
The situation is different with silicon tetrachloride.
The silicon atom is bigger, and so there is more room around it for the water molecule to
attack, and the transition state will be less cluttered.
But silicon has the additional advantage that there are empty 3d orbitals available to accept
a lone pair from the water molecule. Carbon doesn't have 2d orbitals because there are no
such things. There are no empty 2-level orbitals available in the carbon case.
This means that the oxygen can bond to the silicon before the need to break a siliconchlorine bond. This makes the whole process energetically easier.
So . . . silicon tetrachloride reacts violently with water to give white solid silicon dioxide and
steamy fumes of HCl.

Liquid SiCl4 fumes in moist air for this reason - it is reacting with water vapour in the air.

Lead tetrachloride (lead(IV) chloride)


The reaction of lead(IV) chloride with water is just like the silicon tetrachloride one. You will
get lead(IV) oxide produced as a brown solid and fumes of hydrogen chloride given off.
(This will also, of course, be confused by the decomposition of the lead(IV) chloride to give
lead(II) chloride and chlorine gas - see above.)

Lead(II) chloride
Unlike the tetrachlorides, lead(II) chloride can be thought of as ionic. It is sparingly soluble
in cold water, but more soluble in hot water. Looked at simply, solubility in water involves
the break-up of the ionic lattice and the hydration of the lead(II) and chloride ions to give

Pb2+(aq) and Cl-(aq).

THE OXIDES OF GROUP 4

This page takes a brief look at the oxides of carbon, silicon, germanium, tin
and lead. It concentrates on the structural differences between carbon
dioxide and silicon dioxide, and on the trends in acid-base behaviour of the
oxides as you go down Group 4.

The structures of carbon dioxide and silicon dioxide


There is an enormous difference between the physical properties of carbon
dioxide and silicon dioxide (also known as silicon(IV) oxide or silica).
Carbon dioxide is a gas whereas silicon dioxide is a hard high-melting
solid. The other dioxides in Group 4 are also solids.
This obviously reflects a difference in structure between carbon dioxide
and the dioxides of the rest of the Group.
The structure of carbon dioxide
The fact that carbon dioxide is a gas means that it must consist of simple
molecules. Carbon can form simple molecules with oxygen because it can
form double bonds with the oxygen.

None of the other elements in Group 4 form double bonds with oxygen,
and so that forces completely different structures on them.
Note: The explanation for this is quite probably beyond

what you need for the purposes of UK A level chemistry (or


its equivalent), but I am including it anyway. It isn't very
difficult to understand and, to be honest, there isn't anything
else remotely interesting on the rest of this page!
If you can follow it OK, well done! If not, skip over it to the
structure of silicon dioxide. If you haven't met the concept of
hybridisation, it would probably be better to miss it out - but
give it a try and see what happens.

When carbon forms bonds with oxygen, it first promotes one of the electrons in the 2s level
into the empty 2p level. This produces 4 unpaired electrons.

It now reshuffles those electrons slightly by hybridising the 2s electron and one of the 2p
electrons to make two sp1 hybrid orbitals of equal energy. The other 2p electrons are left
alone for the time being.

What these look like in the atom (using the same colour coding) is:

Notice that the two green lobes are two different hybrid orbitals - arranged as far apart from
each other as possible. Don't confuse them with the shape of a p orbital.
So that's how the carbon is organised just before it bonds. Now we need to look at the
oxygen.
Oxygen's electronic structure is 1s22s22px22py12pz1.
Hybridisation occurs in the oxygen as well. This time, sp 2hybrids are formed with the s
orbital and two of the p orbitals being rearranged to give 3 orbitals of equal energy - leaving
a temporarily unaffected p orbital.

This time two of the sp2 hybrid orbitals contain lone pairs of electrons.

Now line up the two oxygens and the carbon prior to bonding them. Notice that the lefthand oxygen has been rotated through 90:

Then bring them together so that the pale green hybrid orbitals overlap end-to-end to form
simple covalent bonds. These are properly called sigma bonds, and are shown as orange
in the next diagram.
This brings the various p orbitals close enough together that they overlap sideways.

Sideways overlap between the two sets of p orbitals produces two pi bonds - similar to the
pi bond found in, say, ethene. These pi bonds are twisted at 90 to each other in the final
molecule.

So . . . in order to form a carbon-oxygen double bond, it is necessary for the p orbitals on


the carbon and the oxygen to overlap sideways.

The structure of silicon dioxide


Silicon doesn't double bond with oxygen.
Silicon atoms are bigger than carbon. That means that silicon-oxygen bonds will be longer
than carbon-oxygen bonds.
Imagine trying to make a silicon-oxygen double bond in the same way as we did for a
carbon-oxygen double bond. With the longer silicon-oxygen bonds, the p orbitals on the
silicon and the oxygen aren't quite close enough together to allow enough sideways
overlap to give a stable pi bond.
So, silicon bonds with oxygen in such a way that only single bonds are formed.
There are various different structures for silicon dioxide. The easiest to remember and draw
is:

This is based on a diamond structure with each of the silicon atoms being bridged to its
other four neighbours via an oxygen atom.
Note: If you want to be fussy, the Si-O-Si bond angles are
wrong in this diagram. In reality the "bridge" from one silicon
atom to its neighbour isn't in a straight line, but via a "V"
shape (similar to the shape around the oxygen atom in a
water molecule). It's extremely difficult to draw that
convincingly and tidily in a diagram involving this number of
atoms. The simplification is perfectly acceptable.

This means that silicon dioxide is a giant covalent structure. The strong bonds in three

dimensions make it a hard, high melting point solid.


Note: If you want a more detailed discussion of the silicon
dioxide structure (including a guide to drawing the diamond
structure!) and how it affects its physical properties, you will
find it on a page about giant covalent structures.
If you choose to follow this link, use the BACK button on
your browser to return to this page.

The acid-base behaviour of the Group 4 oxides


The oxides of the elements at the top of Group 4 are acidic, but acidity of the oxides falls
as you go down the Group. Towards the bottom of the Group, the oxides become more
basic - although without ever losing their acidic character completely.
An oxide which can show both acidic and basic properties is said to be amphoteric.
The trend is therefore from acidic oxides at the top of the Group towards amphoteric ones
at the bottom.

Carbon and silicon oxides


Carbon monoxide
Carbon monoxide is usually treated as if it was a neutral oxide, but in fact it is very, very
slightly acidic. It doesn't react with water, but it will react with hot concentrated sodium
hydroxide solution to give a solution of sodium methanoate.

The fact that the carbon monoxide reacts with the basic hydroxide ion shows that it must
be acidic.

Carbon and silicon dioxides


These are both weakly acidic.
With water
Silicon dioxide doesn't react with water, because of the difficulty of breaking up the giant
covalent structure.
Carbon dioxide does react with water to a slight extent to produce hydrogen ions (strictly,
hydroxonium ions) and hydrogencarbonate ions.
Overall, this reaction is:

The solution of carbon dioxide in water is sometimes known as carbonic acid, but in fact
only about 0.1% of the carbon dioxide has actually reacted. The position of equilibrium is
well to the left-hand side.
With bases
Carbon dioxide reacts with sodium hydroxide solution in the cold to give either sodium
carbonate or sodium hydrogencarbonate solution - depending on the reacting proportions.

Silicon dioxide also reacts with sodium hydroxide solution, but only if it is hot and
concentrated. Sodium silicate solution is formed.

You may also be familiar with one of the reactions happening in the Blast Furnace
extraction of iron - in which calcium oxide (from the limestone which is one of the raw
materials) reacts with silicon dioxide to produce a liquid slag, calcium silicate. This is also
an example of the acidic silicon dioxide reacting with a base.

Germanium, tin and lead oxides


The monoxides
All of these oxides are amphoteric - they show both basic and acidic properties.
The basic nature of the oxides
These oxides all react with acids to form salts.
For example, they all react with concentrated hydrochloric acid. This can be summarised
as:

. . . where X can be Ge and Sn, but unfortunately needs modifying a bit for lead.
Lead(II) chloride is fairly insoluble in water and, instead of getting a solution, it would form
an insoluble layer over the lead(II) oxide if you were to use dilute hydrochloric acid stopping the reaction from going on.

However, in this example we are talking about usingconcentrated hydrochloric acid.


The large excess of chloride ions in the concentrated acid react with the lead(II) chloride to
produce soluble complexes such as PbCl42-. These ionic complexes are soluble in water
and so the problem disappears.

Unfortunately, it means that you have more to remember!


Note: There are almost certainly going to be similar
complexes formed in the germanium and tin cases in the
presence of excess concentrated hydrochloric acid, but
because they aren't important to the reaction happening,
they tend to be ignored at this level.

The acidic nature of the oxides


All of these oxides also react with bases like sodium hydroxide solution. This time we can
generalise without exception:

Lead(II) oxide, for example, would react to give PbO22- - plumbate(II) ions.
Note: This reaction is written using a simplified version of
the formula of the product. This is adequate for this level.

The dioxides
These dioxides are again amphoteric - showing both basic and acidic properties.
The basic nature of the dioxides
The dioxides react with concentrated hydrochloric acid first to give compounds of the type
XCl4:

These will react with excess chloride ions in the hydrochloric acid to give complexes such
as XCl62-.

In the case of lead(IV) oxide, the reaction has to be done with ice-cold hydrochloric acid. If
the reaction is done any warmer, the lead(IV) chloride decomposes to give lead(II) chloride
and chlorine gas. This is an effect of the preferred oxidation state of lead being +2 rather
than +4.
Note: You will find more about this (including an overall
equation for the reaction of lead(IV) oxide with concentrated
hydrochloric acid at ordinary temperatures) on a page about

the oxidation state trends in Group 4.


If you choose to follow this link, use the BACK button on
your browser to return to this page.

The acidic nature of the dioxides


The dioxides will react with hot concentrated sodium hydroxide solution to give soluble
complexes of the form [X(OH)6]2-.

Some sources suggest that the lead(IV) oxide needs molten sodium hydroxide. In that
case, the equation is different.

Note: If you are a UK student doing the Edexcel syllabus,


you might like to know that their chief examiner for A level
chemistry at the time of writing uses this second equation
for the lead(IV) oxide reaction on his website, and the first
equation for the other two dioxides.

SOME INSOLUBLE LEAD(II) COMPOUNDS


This page looks at the formation of some insoluble lead(II) compounds from aqueous
lead(II) ions using precipitation reactions. It describes the reactions to form lead(II)
hydroxide, lead(II) chloride, lead(II) iodide and lead(II) sulphate.
Because of the insolubility of so many lead(II) compounds, the usual source of lead(II) ions
in solution is lead(II) nitrate solution - and that will be assumed in all the following
examples.

Making lead(II) hydroxide


If a little sodium hydroxide solution is added to colourless lead(II) nitrate solution, a white
precipitate of lead(II) hydroxide is produced.

If more sodium hydroxide solution is added, the precipitate redissolves to give a colourless
solution which might be called sodium plumbate(II) solution - but could be called by a lot of
alternative names depending on exactly how the formula is written!

Note: These equations are simplifications. You will get


complexes formed involving hydroxide ions, but the formulae
of these aren't very clear-cut. I am using these particular
versions of the equations to keep them in line with the
corresponding reaction between lead(II) oxide and sodium
hydroxide solution on the oxides of Group 4 page - also a
simplification!

Making lead(II) chloride


Lead(II) chloride can be made as a white precipitate by adding a solution containing
chloride ions to lead(II) nitrate solution. You could use things like sodium chloride solution
to provide the chloride ions, but it is usually easier just to add some dilutehydrochloric acid.

Note: If you add concentrated hydrochloric acid to excess, the


lead(II) chloride precipitate will dissolve again. Complex ions
like PbCl42- are produced, and these are soluble in water.

Making lead(II) iodide

If you add colourless potassium iodide solution (or any other source of iodide ions in
solution) to a solution of lead(II) nitrate, a bright yellow precipitate of lead(II) iodide is
produced.

Making lead(II) sulphate


Adding a source of aqueous sulphate ions to a solution of lead(II) nitrate results in a white
precipitate of lead(II) sulphate. The easiest thing to add is usually dilute sulphuric acid - but
any other soluble sulphate would do.

ATOMIC AND PHYSICAL PROPERTIES OF THE GROUP 7 ELEMENTS (THE


HALOGENS)

This page explores the trends in some atomic and physical properties of
the Group 7 elements (the halogens) - fluorine, chlorine, bromine and
iodine. You will find separate sections below covering the trends in atomic
radius, electronegativity, electron affinity, melting and boiling points, and
solubility. There is also a section on the bond enthalpies (strengths) of
halogen-halogen bonds (for example, Cl-Cl) and of hydrogen-halogen
bonds (e.g. H-Cl)
Even if you aren't currently interested in all these things, it would probably
pay you to read the whole page. The same ideas tend to recur throughout
the atomic properties, and you may find that earlier explanations help to
you understand later ones.

Trends in Atomic Radius


Note: You will find atomic radius covered in detail in another part of this site. If
you choose to follow this link, use the BACK button on your browser to return
quickly to this page.

You can see that the atomic radius increases as you go down the Group.
Explaining the increase in atomic radius
The radius of an atom is governed by

the number of layers of electrons around the nucleus

the pull the outer electrons feel from the nucleus.

Compare fluorine and chlorine:


F

2,7

Cl

2,8,7

In each case, the outer electrons feel a net pull of 7+ from the nucleus. The positive charge
on the nucleus is cut down by the negativeness of the inner electrons.

This is equally true for all the other atoms in Group 7. The outer electrons always feel a net
pull of 7+ from the centre.
The only factor which is going to affect the size of the atom is therefore the number of
layers of inner electrons which have to be fitted in around the atom. Obviously, the more
layers of electrons you have, the more space they will take up - electrons repel each other.
That means that the atoms are bound to get bigger as you go down the Group.

Trends in Electronegativity
Electronegativity is a measure of the tendency of an atom to attract a bonding pair of
electrons. It is usually measured on the Pauling scale, on which the most electronegative
element (fluorine) is given an electronegativity of 4.0.
Note: You will find electronegativity covered in detail in another part of this site. If
you choose to follow this link, use the BACK button on your browser to return
quickly to this page.

Notice that electronegativity falls as you go down the Group. The atoms become less good
at attracting bonding pairs of electrons.
Explaining the decrease in electronegativity
This is easily shown using simple dots-and-crosses diagrams for hydrogen fluoride and
hydrogen chloride.

The bonding pair of electrons between the hydrogen and the halogen feels the same net
pull of 7+ from both the fluorine and the chlorine. (This is exactly the same sort of
argument as you have seen in the atomic radius section above.) However, in the chlorine
case, the nucleus is further away from that bonding pair. That means that it won't be as
strongly attracted as in the fluorine case.
The larger pull from the closer fluorine nucleus is why fluorine is more electronegative than
chlorine is.
Summarising the trend down the Group

As the halogen atoms get bigger, any bonding pair gets further and further away from the
halogen nucleus, and so is less strongly attracted towards it. In other words, as you go
down the Group, the elements become less electronegative.

Trends in First Electron Affinity


Defining first electron affinity
The first electron affinity is the energy released when 1 mole of gaseous atoms each
acquire an electron to form 1 mole of gaseous 1- ions.
This is more easily seen in symbol terms.

It is the energy released (per mole of X) when this change happens.


First electron affinities have negative values. For example, the first electron affinity of
chlorine is -349 kJ mol-1. By convention, the negative sign shows a release of energy.

The first electron affinities of the Group 7 elements


Note: You will find electron affinity covered in detail in another part of this site.
The current page duplicates much of that material, but you might like to read it
again in different words.
If you choose to follow this link, use the BACK button on your browser to return
quickly to this page.

Notice that the trend down the Group isn't tidy. The tendency is for the electron affinities to
decrease (in the sense that less heat is given out), but the fluorine value is out of line.
The electron affinity is a measure of the attraction between the incoming electron and the
nucleus. The higher the attraction, the higher the electron affinity.

In the bigger atom, the attraction from the more positive nucleus is offset by the additional
screening electrons, so each incoming electron feels the effect of a net 7+ charges from
the centre - exactly as when you are thinking about atomic radius or electronegativity.
As the atom gets bigger, the incoming electron is further from the nucleus and so feels less
attraction. The electron affinity therefore falls as you go down the Group.
But what about fluorine? That is a very small atom, with the incoming electron quite close
to the nucleus. Why isn't its electron affinity bigger than chlorine's?
There is another effect operating. When the new electron comes into the atom, it is

entering a region of space already very negatively charged because of the existing
electrons. There is bound to be some repulsion, offsetting some of the attraction from the
nucleus.
In the case of fluorine, because the atom is very small, the existing electron density is very
high. That means that the extra repulsion is particularly great and lessens the attraction
from the nucleus enough to lower the electron affinity below that of chlorine.

Trends in Melting Point and Boiling Point

You will see that both melting points and boiling points rise as you go down the Group.
If you explore the graphs, you will find that fluorine and chlorine are gases at room
temperature, bromine is a liquid and iodine a solid. Nothing very surprising there!
Explaining the trends in melting point and boiling point
All of the halogens exist as diatomic molecules - F2, Cl2, and so on. The intermolecular
attractions between one molecule and its neighbours are van der Waals dispersion forces.
Note: If you aren't sure about van der Waals dispersion forces, you will find them
covered in detail in another part of this site. You won't understand the next bit

unless you are happy about dispersion forces and how they vary with the size of
the molecule.
Use the BACK button on your browser to return quickly to this page.

As the molecules get bigger there are obviously more electrons which can move around
and set up the temporary dipoles which create these attractions.
The stronger intermolecular attractions as the molecules get bigger means that you have to
supply more heat energy to turn them into either a liquid or a gas - and so their melting and
boiling points rise.

Solubilities
Solubility in water
Fluorine reacts violently with water to give hydrogen fluoride gas (or a solution of
hydrofluoric acid) and a mixture of oxygen and ozone. So thinking about its solubility is
pointless.
Chlorine, bromine and iodine all dissolve in water to some extent, but there is no pattern in
this. The following table shows the solubility of the three elements in water at 25C.
solubility
(mol dm-3)
chlorine

0.091

bromine

0.21

iodine

0.0013
Note: These figures come from page 476 of Advanced Inorganic Chemistry (third
edition) by Cotton and Wilkinson.

Chlorine solution in water is pale green. Bromine solution in water is anything from yellow
to dark orange-red depending on how concentrated it is. Iodine solution in water is very
pale brown.
Chlorine reacts with water to some extent to give a mixture of hydrochloric acid and
chloric(I) acid - also known as hypochlorous acid. The reaction is reversible, and at any
one time only about a third of the chlorine molecules have actually reacted.

You will sometimes find the chloric(I) acid written as HOCl. That represents the way the
atoms are actually joined together.
Bromine and iodine do something similar, but to a much lesser extent. In both cases, about
99.5% of the halogen remains as unreacted molecules.
The solubility of iodine in potassium iodide solution
Although iodine is only faintly soluble in water, it does dissolve freely in potassium iodide
solution to give a dark red-brown solution. There is a reversible reaction between iodine
molecules and iodide ions to give I3- ions. These are responsible for the colour.
In the lab, iodine is often produced by oxidation of a solution containing iodide ions, so this
colour is actually quite familiar. As long as there are any excess iodide ions present, the
iodine will react with them to make the I3- ions. Once the iodide ions have all reacted, the
iodine is precipitated as a dark grey solid, because there isn't anything left for it to react
with to keep it in solution.

Solubility in hexane
The halogens are much more soluble in organic solvents like hexane than they are in
water. Both hexane and the halogens are non-polar molecules attracted to each other by
van der Waals dispersion forces.
That means that the attractions broken (between hexane molecules and between halogen

molecules) are similar to the new attractions made when the two substances mix.
The colours of the solutions formed are much what you would expect. Solutions of iodine in
organic solvents tend to be pinky-purple colour.

Bond enthalpies (bond energies or bond strengths)


Bond enthalpy is the heat needed to break one mole of a covalent bond to produce
individual atoms, starting from the original substance in the gas state, and ending with
gaseous atoms.
So for chlorine, Cl2(g), it is the heat energy needed to carry out this change per mole of
bond:

For bromine, the reaction is still from gaseous bromine molecules to separate gaseous
atoms.

Bond enthalpy in the halogens, X2(g)


A covalent bond works because the bonding pair is attracted to both the nuclei at either
side of it. It is that attraction which holds the molecule together. The size of the attraction
will depend, amongst other things, on the distance from the bonding pair to the two nuclei.

As with all halogens, the bonding pair will feel a net pull of 7+ from both ends of the bond the charge on the nucleus offset by the inner electrons. That will still be the same whatever
the size of the halogen atoms.
As the atoms get bigger, the bonding pair gets further from the nuclei and so you would
expect the strength of the bond to fall.

So . . . are the actual bond enthalpies in line with this prediction?

The bond enthalpies of the Cl-Cl, Br-Br and I-I bonds fall just as you would expect, but the
F-F bond is way out of line!
Because fluorine atoms are so small, you might expect a very strong bond - in fact, it is
remarkably weak. There must be another factor at work as well.
As well as the bonding pair of electrons between the two atoms, each atom has 3 nonbonding pairs of electrons in the outer level - lone pairs. Where the bond gets very short
(as in F-F), the lone pairs on the two atoms get close enough together to set up a
significant amount of repulsion.

In the case of fluorine, this repulsion is great enough to counteract quite a lot of the

attraction between the bonding pair and the two nuclei. This obviously weakens the bond.

Bond enthalpies in the hydrogen halides, HX(g)


Where the halogen atom is attached to a hydrogen atom, this effect doesn't happen. There
are no lone pairs on a hydrogen atom!

As the halogen atom gets bigger, the bonding pair gets more and more distant from the
nucleus. The attraction is less, and the bond gets weaker - exactly what is shown by the
data. There is nothing complicated happening in this case.
This is important in the thermal stability of the hydrogen halides - how easily they are
broken up into hydrogen and the halogen on heating.
Hydrogen fluoride and hydrogen chloride are very stable to heat. They don't split up into
hydrogen and fluorine or chlorine again if heated to any normal lab temperature.
Hydrogen bromide splits slightly into hydrogen and bromine on heating, and hydrogen
iodide splits to an even greater extent.
As the bonds get weaker, they are more easily broken.
Note: Breaking the hydrogen-halogen bond is only one of the steps in the overall
reaction, of course. You don't end up with hydrogen atoms and halogen atoms -

you get diatomic molecules, H2 and X2. If you have done some energetics
calculations, it would be a useful exercise to use bond enthalpies and atomisation
enthalpies to calculate the overall enthalpy changes for the decomposition of the
hydrogen halides.
(Remember that bond enthalpies only apply to substances in the gas state, and
bromine and iodine would end up as liquid and solid respectively. Using
atomisation enthalpies for the halogens avoids this problem. If you don't
understand what I am talking about, you don't yet have enough knowledge to be
able to do this.)

HE OXIDISING ABILITY OF THE GROUP 7 ELEMENTS


(THE HALOGENS)
This page explores the trend in oxidising ability of the Group 7 elements (the halogens) fluorine, chlorine, bromine and iodine. We are going to look at the ability of one halogen to
oxidise the ions of another one, and how that changes as you go down the Group.
Note: If you aren't comfortable with terms like oxidation and oxidising agent in
terms of electron transfer, then you should explore the area of the site dealing
with redox reactionsbefore you go on.

The facts
We are going to look at the reactions between one halogen (chlorine, say) and the ions of
another one (iodide ions, perhaps). The iodide ions will be in a solution of a salt like
sodium or potassium iodide. The sodium or potassium ions will be spectator ions, and are
completely irrelevant to the reaction.
In the chlorine and iodide ion case, the reaction would be:

The iodide ions have lost electrons to form iodine molecules. They have been oxidised.
The chlorine molecules have gained electrons to form chloride ions. They have been
reduced.
This is obviously a redox reaction in which chlorine is acting as an oxidising agent.
Fluorine
We'll have to exclude fluorine from this descriptive bit, because it is too strong an oxidising
agent. Fluorine oxidises water to oxygen and so it is impossible to do simple solution
reactions with it.

Chlorine, bromine and iodine


In each case, a halogen higher in the Group can oxidise the ions of one lower down. For
example, chlorine can oxidise the bromide ions (in, for example, potassium bromide
solution) to bromine:

The bromine appears as an orange solution.


As you have seen above, chlorine can also oxidise iodide ions (in, for example, potassium
iodide solution) to iodine:

The iodine appears either as a red solution if you are mean with the amount of chlorine you
use, or as a dark grey precipitate if the chlorine is in excess.
Note: The reason for the red solution is that iodine dissolves in potassium
iodide (or other soluble iodides) by reacting to give a red ion, I 3-. If the chlorine
is in excess, obviously there isn't anything left for the iodine to react with, and
so it remains as a dark grey precipitate.

Bromine can only oxidise iodide ions to iodine. It isn't a strong enough oxidising agent to
convert chloride ions into chlorine. (You have just seen exactly the reverse of that
happening.)
A red solution of iodine is formed (see the note above) until the bromine is in excess. Then
you get a dark grey precipitate.

Iodine won't oxidise any of the other halide ions (unless you happened to have some
extremely radioactive and amazingly rare astatide ions - astatine is at the bottom of this
Group).
To summarise

Oxidation is loss of electrons. Each of the elements (for example, chlorine) could
potentially take electrons from something else to make their ions (e.g. Cl -). That
means that they are all potentially oxidising agents.

Fluorine is such a powerful oxidising agent that you can't reasonably do solution
reactions with it.

Chlorine has the ability to take electrons from both bromide ions and iodide ions.
Bromine and iodine can't get those electrons back from the chloride ions formed.
That means that chlorine is a more powerful oxidising agent than either bromine or
iodine.

Similarly bromine is a more powerful oxidising agent than iodine. Bromine can
remove electrons from iodide ions to give iodine - and the iodine can't get them back
from the bromide ions formed.

This all means that oxidising ability falls as you go down the Group.

Explaining the trend


Whenever one of these halogens is involved in oxidising something in solution, the halogen

ends up as halide ions with water molecules attached to them. Looking at all four of the
common halogens:

As you go down the Group, the ease with which these hydrated ions are formed falls, and
so the halogens become less good as oxidising agents - less ready to take electrons from
something else.
The reason that the hydrated ions form less readily as you go down the Group is a fairly
complicated mixture of several factors. Unfortunately, this is often over-simplified to give
what is actually a faulty and misleading explanation. We'll deal with this first before giving a
proper explanation.
The faulty explanation
This is normally given for the trend in oxidising ability of chlorine, bromine and iodine, and
goes like this:
How easily the element forms its ions depends on how strongly the new electrons are
attracted. As the atoms get bigger, the new electrons find themselves further from the
nucleus, and more and more screened from it by the inner electrons (offsetting the effect of
the greater nuclear charge). The bigger atoms are therefore less good at attracting new
electrons and forming ions.
That sounds reasonable! What's wrong with it?
What we are describing is the trend in electron affinity as you go from chlorine to bromine
to iodine. Electron affinity tends to fall as you go down the Group. This is described in detail
on another page.
Note: If you haven't recently read about the electron affinities of the halogens,
you ought to follow this link before you go on.

Use the BACK button on your browser to return to this page.

The snag comes if you try to expand the argument to include fluorine. Fluorine has a much
higher tendency to form its hydrated ion than chlorine does. BUT . . . the tendency of the
fluorine atom to gain an electron is less than that of chlorine - as measured by its electron
affinity! That makes a nonsense of the whole argument.
So, what is going wrong? The mistake is to look at only one part of a much more
complicated process. The argument about atoms accepting electrons applies to isolated
atoms in the gas state picking up electrons to make isolated ions - also in the gas state.
That's not what we should be talking about.
In reality:

The halogen starts as diatomic molecules, X2 - which may be gas, liquid or solid,
depending on the halogen.

These have to be split apart to make individual atoms.

Those atoms each gain an electron. (That's the stage of the process we've been
concentrating on in the faulty explanation.)

The isolated ions become wrapped in water molecules to form hydrated ions.

Note: For the next bit, if you aren't happy about enthalpy changes, you might
want to explore the energetics section of Chemguide, or my chemistry
calculations book.

The proper explanation


The table below looks at how much energy is involved in each of these changes. To be
sure that you understand the various terms:

Atomisation energy
This is the energy needed to produce 1 mole of isolated gaseous atoms starting
from an element in its standard state (gas for chlorine, and liquid for bromine, for
example - both of them as X2).
For a gas like chlorine, this is simply half of the bond enthalpy (because breaking a
Cl-Cl bond produces 2 chlorine atoms, not 1). For a liquid like bromine or a solid like
iodine, it also includes the energy that is needed to convert them into gases.
Electron affinity
The first electron affinity is the energy released when 1 mole of gaseous atoms each
acquire an electron to form 1 mole of gaseous 1- ions.
In symbol terms:

Hydration enthalpy (hydration energy)


This is the energy released when 1 mole of gaseous ions dissolves in water to
produce hydrated ions.

atomisation energy
(kJ mol-1)

electron
affinity
(kJ mol-1)

hydration
enthalpy
(kJ mol-1)

overall
(kJ mol-1)

+79

-328

-506

-755

Cl

+121

-349

-364

-592

Br

+112

-324

-335

-547

+107

-295

-293

-481

There's quite a lot of data here to look at. Concentrate first on the final column which
shows the overall heat evolved when all the other processes happen. It is calculated by
adding the figures in the previous 3 columns.
You can see that the amount of heat evolved falls quite dramatically from the top to the
bottom of the Group, with the biggest fall from fluorine to chlorine.
Fluorine produces a lot of heat when it forms its hydrated ion, chlorine less so, and so on
down the Group.
Note: Don't forget that we are only talking about half of a redox reaction in
each case. There will be other energy terms involving whatever the halogen is
oxidising. Those changes will be overall endothermic. For example, if chlorine
oxidises iodide ions to iodine, that half of the total reaction would need +481 kJ
mol-1, giving an enthalpy change of reaction of (-592 + 481) = -111 kJ per mole
of I- oxidised.

Why is fluorine a much stronger oxidising agent than chlorine?


What produces the very negative value for the enthalpy change when fluorine turns into its
hydrated ions? There are two main factors.
The atomisation energy of fluorine is abnormally low. This reflects the low bond enthalpy of
fluorine.
Note: The reason for fluorine's low bond enthalpy is described on another
page.

The main reason, though, is the very high hydration enthalpy of the fluoride ion. That is
because the ion is very small. There is a very strong attraction between the fluoride ions
and water molecules. The stronger the attraction, the more heat is evolved when the
hydrated ions are formed.
Why the fall in oxidising ability from chlorine to bromine to iodine?

The fall in atomisation energy between these three elements is fairly slight, and would tend
to make the overall change more negative as you go down the Group. The explanation
doesn't lie there!
It is helpful to look at the changes in electron affinity and hydration enthalpy as you go
down the Group. Using the figures from the previous table:
change in electron affinity
(kJ mol-1)

change in hydration enthalpy


(kJ mol-1)

Cl to Br

+25

+29

Br to I

+29

+42

going from

You can see that both of these effects matter, but that the more important one - the one
that changes the most - is the change in the hydration enthalpy.
As you go down the Group, the ions become less attractive to water molecules as they get
bigger. Although the ease with which an atom attracts an electron matters, it isn't actually
as important as the hydration enthalpy of the negative ion formed.
The faulty explanation misses the mark even if you restrict it to chlorine, bromine and
iodine!
Warning! You really need to find out what (if any) explanation your examiners
expect you to give for this. If their mark schemes (or the way they phrase their
questions) suggest that they want the faulty explanation, there isn't much you
can do about it. Unfortunately, there are times in exams when you have to grit
your teeth and give technically wrong answers because that's what your
examiners want. It shouldn't happen like this, but it does!
UK A' level students should search their syllabuses, past exam papers, mark
schemes and any other support material available from their Exam Board. If
you haven't got any of this, you can find your Exam Board's web address by
following this link. Students elsewhere should find out the equivalent
information from their own sources.

ASSORTED REACTIONS OF THE HALOGENS


This page describes an assortment of reactions of the halogens which don't fit tidily in
other pages in this section. All the reactions of the halogens described are redox reactions.

Reactions with hydrogen


This shows the fall in reactivity of the halogens as you go down Group 7.
Fluorine combines explosively with hydrogen even in the cold and dark to give hydrogen
fluoride gas.
Chlorine and hydrogen explode if exposed to sunlight or a flame to give hydrogen chloride
gas. Alternatively, you can make them combine more peacefully if you light a jet of
hydrogen and then lower it into a gas jar of chlorine. The hydrogen continues to burn and
hydrogen chloride gas is again formed.
Bromine vapour and hydrogen combine with a mild explosion if you put a flame in.
Hydrogen bromide gas is formed.
Iodine and hydrogen only combine partially even on constant heating. An equilibrium is set
up between the hydrogen and the iodine and hydrogen iodide gas.
All of these have an equation of the form:

. . . except the iodine case where you would have to replace the arrow by a reversible sign.

Reactions with phosphorus


Warning! You have to be careful in comparing the rates of these reactions because you

won't necessarily be comparing like with like. For example, it wouldn't be fair to compare
the rate at which phosphorus reacted with gaseous chlorine with the rate it reacted with
liquid bromine. There would be much more contact between the particles with the
phosphorus and the liquid bromine than between phosphorus and chlorine gas.

The formation of trihalides, PX3


All of the halogens react with phosphorus to give, in the first instance, phosphorus(III)
halides - PX3.
There are two common forms of phosphorus which you might come across in the lab white phosphorus (sometimes called yellow phosphorus) and red phosphorus. The white
phosphorus is more reactive than red phosphorus.
To see the reaction between red phosphorus and bromine, you might like to look at
this short bit of video on YouTube. You can see that this is a violent reaction in the cold.
You would expect white phosphorus to behave even more dramatically.
When you write equations for these reactions, you have to be careful how you write the
phosphorus. White phosphorus is molecular, consisting of P 4 molecules. Red phosphorus
is polymeric, and you just use the symbol P.
So if you were writing the equation for the reaction between white phosphorus and
bromine, you would write:

. . . and for red phosphorus:

The formation of pentahalides, PX5


In an excess of chlorine or bromine, phosphorus reacts to form phosphorus(V) chloride or

bromide. Most simply, using white phosphorus:

There is actually a reversible reaction involving phosphorus(III) chloride and phosphorus(V)


chloride.

An excess of chlorine obviously pushes this equilibrium to the right.


Phosphorus and iodine don't seem to form a pentaiodide. The probable reason is that you
can't fit five large iodine atoms around the central phosphorus atom.
I haven't been able to find out for sure whether you can make phosphorus(V) fluoride by
reacting phosphorus with fluorine. Phosphorus(V) fluoride certainly exists, but I can't find
any reference to it being made by direct combination of phosphorus and fluorine.

Reactions with sodium


All of the halogens react with sodium to produce sodium halides. You are probably familiar
with the bright orange flame you get if you lower hot sodium into a gas jar of chlorine gas,
giving white sodium chloride as the product.

Hot sodium will also burn in bromine or iodine vapour to produce sodium bromide or
sodium iodide. In each case, you would get an orange flame and a white solid product.
I would imagine that sodium would burn in fluorine without heating to give sodium fluoride,
although I have never seen it done.

Reactions with iron


With the exception of iodine, iron burns in the halogen vapour to give iron(III) halides.

Iodine is less reactive, and only produces iron(II) iodide.


Fluorine
Cold iron wool burns in cold fluorine to give iron(III) fluoride. Anhydrous iron(III) fluoride is
variously described as white or pale green. Cotton and Wilkinson (a standard degree level
inorganic textbook) describes it as white.

This is a rapid reaction (the iron burns), and the iron has been oxidised to an iron(III)
compound - in other words, from an oxidation state of zero in the iron metal to an oxidation
state of +3 in the iron(III) compound.
Note: If you have forgotten about oxidation states
(oxidation numbers), now is the time to revise them.

Chlorine
If you pass chlorine gas over hot iron, the iron burns to form iron(III) chloride. Iron(III)
chloride forms black crystals if it is anhydrous. Any trace of water present in the apparatus,
or in the chlorine, reacts with this to give reddish-brown colours.

The iron has been oxidised from an oxidation state of zero to +3.
Bromine
If you pass bromine vapour over hot iron, a similar but slightly less vigorous reaction
happens, this time producing iron(III) bromide. Anhydrous iron(III) bromide is usually
produced as a reddish-brown solid.

Again the iron has been oxidised to an oxidation state of +3.


Iodine
The reaction between hot iron and iodine vapour only produces iron(II) iodide, and is much
less vigorous. The iron(II) iodide is said to be grey. If you do this reaction, the product is
always contaminated with iodine, so it is difficult to be sure.

This time, the iodine is only capable of oxidising the iron as far as the +2 oxidation state.

Reactions with solutions containing iron(II) ions


This time, we can only talk about the reactions of chlorine, bromine and iodine. Wherever
you have solutions, fluorine will react with the water.
Chlorine and bromine are strong enough oxidising agents to oxidise iron(II) ions to iron(III)
ions. In the process, the chlorine is reduced to chloride ions; the bromine to bromide ions.
It is easiest to see this with ionic equations:

For the bromine equation, just swap Cl for Br.


The very pale green solution containing the iron(II) ions will turn into a yellow or orange
solution containing iron(III) ions.

Iodine isn't a strong enough oxidising agent to oxidise iron(II) ions, so there is no reaction.
In fact the reverse reaction happens. Iron(III) ions are strong enough oxidising agents to

oxidise iodide ions to iodine:

Reactions with sodium hydroxide solution


Once again, we will just look at this for chlorine, bromine and iodine. We will start by
looking at the chlorine case in detail because it is the one you are most likely to come
across.

The reaction of chlorine with cold sodium hydroxide solution


The reaction between chlorine and cold dilute sodium hydroxide solution is:

NaClO (sometimes written as NaOCl) is sodium chlorate(I). The old name for this is
sodium hypochlorite - and the solution on the right-hand side of the equation is what is
normally sold as bleach.
Now, think about this in terms of oxidation states.
Obviously the chlorine has changed oxidation state because it has ended up in compounds
starting from the original element. Checking all the oxidation states shows:

The chlorine is the only thing to have changed oxidation state. Has it been oxidised or
reduced? Yes! Both! One atom has been reduced because its oxidation state has fallen.
The other has been oxidised.
This is a good example of a disproportionation reaction. A disproportionation reaction is

one in which a single substance is both oxidised and reduced.

The reaction of chlorine with hot sodium hydroxide solution


The reaction between chlorine and hot concentrated sodium hydroxide solution is:

The unfamiliar product this time is sodium chlorate(V) - NaClO 3.


As before, check the oxidation states of everything in the equation. Once again, you will
find that the only thing to have changed is the chlorine. It goes from 0 in the chlorine
molecules on the left-hand side to -1 (in the NaCl) and +5 (in the NaClO 3).
This is also a disproportionation reaction.

Building equations for these reactions


Actually, the first one is simple, and most people would just write it down. The second one
is more difficult, and one way of building it up is using oxidation states.
You would need to have learnt the two main products of the reaction. So write those down:

Now think about the oxidation state changes. To go to NaCl, the oxidation state of the
chlorine has fallen from 0 to -1.
To go to NaClO3, it has increased from 0 to +5.
The positive and negative oxidation state changes must cancel out, so for every
NaClO3 formed, there must be 5 NaCl. Write that down:

Now it is a simple job to balance the sodiums and the chlorines. When you have finished,
you will find that you have enough hydrogens and oxygens left over to make 3H 2O. That

seems reasonable!

The reactions involving bromine and iodine


These are essentially similar to the chlorine, the difference being the temperatures at which
things happen. The tendency to form the ion with the halogen in the +5 oxidation state
increases rapidly as you go down the Group.
Bromine and sodium hydroxide solution
With bromine, the formation of the sodium bromate(V) happens at a much lower
temperature, down to room temperature. If you want to make a solution of sodium
bromate(I), you have to do the reaction at about 0C.
Iodine and sodium hydroxide solution
In this case, you get sodium iodate(V) whatever the temperature. Cotton and Wilkinson
(Advanced Inorganic Chemistry 3rd edition page 477) say that the iodate(I) ion is unknown
in solution.
THE ACIDITY OF THE HYDROGEN HALIDES

This page looks at the acidity of the hydrogen halides - hydrogen fluoride, hydrogen
chloride, hydrogen bromide and hydrogen iodide. It starts by describing their
physical properties and how they might be made and then explains what happens
when they react with water to make acids like hydrofluoric acid and hydrochloric
acid.

The hydrogen halides - background information


Physical properties

The hydrogen halides are colourless gases at room temperature, producing steamy
fumes in moist air. Hydrogen fluoride has an abnormally high boiling point for the
size of the molecule (293 K or 20C), and could condense to a liquid on a cool day.

Hydrogen fluoride's boiling point is higher than you might expect because it forms
hydrogen bonds.
Note: If you aren't happy about hydrogen bonding, you ought to
follow this link before you go on.
Use the BACK button on your browser to return to this page.

Fluorine is the most electronegative of all the elements and the bond between it and
hydrogen is very polar. The hydrogen atom carries quite a lot of positive charge ( +); the
fluorine is fairly negatively charged ( -).
In addition, each fluorine atom has 3 very active lone pairs of electrons. Fluorine's outer
electrons are at the 2-level, and the lone pairs represent small highly charged regions of
space. Hydrogen bonds form between the + hydrogen on one HF molecule and a lone
pair on the fluorine of another one.

The other hydrogen halides don't form hydrogen bonds. The other halogens aren't as
electronegative as fluorine, and so the bonds in HX are less polar. As well as that, their
lone pairs are at higher energy levels. That makes the lone pairs bigger, and so they don't
carry such an intensely concentrated negative charge for the hydrogens to be attracted to.
Note: If you aren't sure about why the electronegativity of the
halogens changes as you go down the Group, you could follow this
link.
Use the BACK button on your browser to return to this page.

Making the hydrogen halides


There are several ways of making hydrogen halides, but the only one of interest at A' level
is the reaction between an ionic halide (like sodium chloride) and an acid like concentrated
phosphoric(V) acid, H3PO4, or concentrated sulphuric acid.
Making hydrogen chloride
You can add concentrated sulphuric acid to a solid chloride like sodium chloride in the cold.
The concentrated sulphuric acid donates a hydrogen ion to a chloride ion to make
hydrogen chloride. Because this is a gas, it immediately escapes from the system.

The full equation for the reaction is:

Sodium hydrogensulphate is also formed.


Concentrated phosphoric(V) acid behaves similarly. You would again add it to solid sodium
choride. Once again, as soon as any hydrogen chloride is formed, it escapes as a gas. The
ionic equation is:

. . . and the full one showing the formation of the salt, sodium dihydrogenphosphate(V) is:

Making the other hydrogen halides


All of the hydrogen halides can be made in an exactly similar way using concentrated
phosphoric(V) acid. All you would need to do is swap the symbol Cl in the two equations
for whichever other halogen you were interested in.
The situation is more complicated with concentrated sulphuric acid.
Hydrogen fluoride can be made in exactly the same way as hydrogen chloride using
concentrated sulphuric acid, but hydrogen bromide and hydrogen iodide can't.
The problem is that concentrated sulphuric acid is a reasonably strong oxidising agent, and
as well as producing hydrogen bromide or hydrogen iodide, some of the halide ions are
oxidised to bromine or iodine. This problem doesn't happen with phosphoric(V) acid
because it isn't an oxidising agent.
Note: Redox reactions involving halide ions and conc sulphuric
acid are covered on a separate page.

The acidity of the hydrogen halides

Hydrogen chloride as an acid


We are going to use the Bronsted-Lowry definition of an acid as a proton donor. Hydrogen
chloride is an acid because it gives protons (hydrogen ions) to other things. We are going
to concentrate on its reaction with water.
Hydrogen chloride gas is very soluble in water, reacting with it to produce hydrochloric acid.
The familiar steamy fumes of hydrogen chloride in moist air are caused by the hydrogen
chloride reacting with water vapour in the air to produce a fog of concentrated hydrochloric
acid.
A proton is donated from the hydrogen chloride to one of the lone pairs on a water
molecule.

A co-ordinate (dative covalent) bond is formed between the oxygen and the transferred
hydrogen ion.
Note: If you need to revise co-ordinate (dative covalent) bonding, you
could follow this link. That page also describes the reaction between
hydrogen chloride and ammonia - another reaction of hydrogen
chloride as an acid.
Use the BACK button on your browser to return to this page.

The equation for the reaction is:

The H3O+ ion is the hydroxonium ion (also known as the hydronium ion or the oxonium ion).

This is the ion that we are actually talking about when we write H +(aq).
When hydrogen chloride dissolves in water (to produce hydrochloric acid), almost 100% of
the hydrogen chloride molecules react in this way. Hydrochloric acid is therefore astrong
acid. A strong acid is one which is fully ionised in solution.
Hydrobromic acid and hydriodic acid as strong acids
Hydrogen bromide and hydrogen iodide dissolve in (and react with) water in exactly the
same way as hydrogen chloride does. Hydrogen bromide reacts to give hydrobromic acid;
hydrogen iodide gives hydriodic acid. Both of these are also strong acids.
Hydrofluoric acid as an exception
By contrast, although hydrogen fluoride dissolves freely in water, hydrofluoric acid is only a
weak acid - similar in strength to organic acids like methanoic acid.
In the past, the explanation for this was often given as the very high strength of the H-F
bond, which has to be broken when hydrogen fluoride forms ions. But this explanation falls
to pieces if you look at the energetics of the reaction in detail.
It is always dangerous to look at the energetics of just one step in the whole series of
energy changes which happen during a reaction.
In this case, you do indeed have to put a lot of energy in to break the hydrogen-fluorine
bond, but you also get a very large amount of energy released when the fluoride ion
becomes surrounded by water molecules in solution. The high hydration enthalpy of the
fluoride ion more or less compensates for the high H-F bond strength.
Up to September 2014, this Chemguide page looked at the energetics of this in scary
detail, but by accident I then came across a much better explanation of why hydrofluoric
acid is weak, which is quite easy to understand:
Why hydrofluoric acid is weak
There is good spectroscopic evidence that hydrogen fluoride ionises fairly completely in
solution in water, but instead of producing free hydroxonium ions, H 3O+, and fluoride ions,
there is such strong attraction between these that they form a strongly bound ion pair,

H3O+.F-

The position of this equilibrium lies well to the right.


But to function as an acid, the hydroxonium ion needs to be free - not attached firmly to a
fluoride ion,

and this equilibrium lies much further to the left.


So hydrofluoric acid is weak, not because ionisation is weak, but because the ions formed
bind themselves together too strongly.
Note: If you want to follow this up, you will find a research article on
this page from the Journal of the American Chemical Society. This
will give you the first page of the article, which contains enough
information for this level. If you have the right access, you can, of
course, read the whole thing.

THE REDOX REACTIONS BETWEEN HALIDE IONS AND


CONCENTRATED SULPHURIC ACID
This page describes and explains the redox reactions involving halide ions and
concentrated sulphuric acid. It uses these reactions to discuss the trend in reducing ability
of the ions as you go from fluoride to chloride to bromide to iodide.

The Facts
There are two different types of reaction which might go on when concentrated sulphuric
acid is added to a solid ionic halide like sodium fluoride, chloride, bromide or iodide. The

concentrated sulphuric acid can act both as an acid and as an oxidising agent.
Concentrated sulphuric acid acting as an acid
The concentrated sulphuric acid gives a hydrogen ion to the halide ion to produce a
hydrogen halide. Because this is a gas, it immediately escapes from the system. If the
hydrogen halide is exposed to moist air, you see it as steamy fumes.
As an example, concentrated sulphuric acid reacts with solid sodium chloride in the cold to
produce hydrogen chloride and sodium hydrogensulphate.

All of the halide ions (fluoride, chloride, bromide and iodide) behave similarly.
Note: These reactions to make the hydrogen halides are dealt with on a separate
page.
If you want to read a bit more about them, follow this link and use the BACK button
on your browser to return to this page.

Concentrated sulphuric acid acting as an oxidising agent


With fluoride or chloride ions
Concentrated sulphuric acid isn't a strong enough oxidising agent to oxidise fluoride or
chloride ions. In those cases, all you get produced are the steamy fumes of the hydrogen
halide - hydrogen fluoride or hydrogen chloride.
You can look at this another way - from the point of view of the halide ions. The fluoride
and chloride ions aren't strong enough reducing agents to reduce the sulphuric acid.
Whichever way you look at it, all you get is the hydrogen halide!
That isn't true, though, with bromides and iodides.

With bromide ions


The bromide ions are strong enough reducing agents to reduce the concentrated sulphuric
acid. In the process the bromide ions are oxidised to bromine.

The bromide ions reduce the sulphuric acid to sulphur dioxide gas. This is a decrease of
oxidation state of the sulphur from +6 in the sulphuric acid to +4 in the sulphur dioxide.

You can combine these two half-equations to give the overall ionic equation for the
reaction:

Note: If you aren't confident about redox reactions, electron-half equations, and
oxidation states you really ought to follow this link before you go any further.

What you see in this reaction are the steamy fumes of hydrogen bromide contaminated
with the brown colour of bromine vapour. The sulphur dioxide is a colourless gas, so you
couldn't observe its presence directly.
With iodide ions
Iodide ions are stronger reducing agents than bromide ions are. They are oxidised to iodine
by the concentrated sulphuric acid.

The reduction of the sulphuric acid is more complicated than before. The iodide ions are
powerful enough reducing agents to reduce it

first to sulphur dioxide (sulphur oxidation state = +4)

then to sulphur itself (oxidation state = 0)

and all the way to hydrogen sulphide (sulphur oxidation state = -2).

The most important of this mixture of reduction products is probably the hydrogen sulphide.
The half-equation for its formation is:

Combining these last two half-equations gives:

Important! Don't try to remember this equation - the chances of you ever needing it
in an exam are tiny. Learn how to work out electron-half-equations and combine
them to make the overall equation. A bit of time acquiring that skill will save you a lot
of pointless learning.

This time what you see is a trace of steamy fumes of hydrogen iodide, but mainly lots of
iodine. The reaction is exothermic and so purple iodine vapour is formed, and probably
dark grey solid iodine condensing around the top of the tube. There will also be red colours
where the iodine comes into contact with the solid iodide.
The red colour is due to the I3- ion formed by reaction between I2 molecules and I- ions.
You won't see the colourless hydrogen sulphide gas, but might pick up its "bad egg" smell
if you were foolish enough to smell the intensely poisonous gases evolved!

Summary of the trend in reducing ability

Fluoride and chloride ions won't reduce concentrated sulphuric acid.

Bromide ions reduce the sulphuric acid to sulphur dioxide. In the process, the
bromide ions are oxidised to bromine.

Iodide ions reduce the sulphuric acid to a mixture of products including hydrogen
sulphide. The iodide ions are oxidised to iodine.

Reducing ability of the halide ions increases as you go down the Group.

Explaining the trend


An over-simplified explanation
This only works (and even then, not very well!) if you ignore fluoride ions. The argument
goes like this:
When a halide ion acts as a reducing agent, it gives electrons to something else. That
means that the halide ion itself has to lose electrons.
The bigger the halide ion, the further the outer electrons are from the nucleus, and the
more they are screened from it by inner electrons. It therefore gets easier for the halide
ions to lose electrons as you go down the Group because there is less attraction between
the outer electrons and the nucleus.
It sounds convincing, but it only tells part of the story. We need to look in some detail at the
energetics of the change.
Important! You really need to find out what (if any) explanation your examiners
expect you to give for this. If their mark schemes (or the way they phrase their
questions) suggest that they want this simplified explanation, then that's what you
will have to give them.
The rest of this page is going to get quite complicated. It would be worth while
finding out whether it is something youneed to know. (Although it is always more
satisfying the closer you can get to the truth!)
UK A' level students should search their syllabuses, past exam papers, mark
schemes and any other support material available from their Exam Board. If you
haven't got any of this, you can find your Exam Board's web address by following
this link. Students elsewhere should find out the equivalent information from their
own sources.

A more detailed explanation


Looking at how the enthalpy changes vary from halogen to halogen
We need to compare the amount of heat evolved or absorbed when you convert a solid
halide (like sodium chloride) into molecules of the halogen.
Taking sodium chloride as an example:

We need to supply the energy to break the attractions between the ions in the
sodium chloride. In other words, we need to supply the lattice enthalpy.

We need to supply the energy to remove the electron from the chloride ion. This is
the reverse of the electron affinity of the chlorine. You can get this figure by looking
up the electron affinity in a Data Book and giving it a positive rather than a negative
sign.

We then recover some energy when the chlorine atoms turn into chlorine molecules.
Energy is released when the bonds are formed.
Chlorine is simple because it is a gas. With bromine and iodine, heat will also be
released when they condense to a liquid or solid. To take account of this, it is better
to think of this in terms of atomisation energy rather than bond energy. The number
we want is the reverse of atomisation energy.
Atomisation energy is the energy needed to produce 1 mole of isolated gaseous
atoms starting from an element in its standard state (gas for chlorine, and liquid for
bromine, for example - both of them as X2).

Look carefully at the diagram so that you see how this all fits together:

Note: The term "lattice enthalpy" used here should more accurately be described
as "lattice dissociation enthalpy".
If you aren't confident about energy cycles and the logic behind them (Hess's Law),
you might want to explore theenergetics section of Chemguide, or my chemistry
calculations book.

What we need to do is calculate the enthalpy change shown by the green arrow in the
diagram for each of the halogens so that we can make a comparison. The diagram shows
that the overall change involving the halide ions is endothermic - the green arrow is
pointing upwards towards a higher energy.
This isn't the total enthalpy change for the whole reaction. Heat will be given out when the
changes involving the sulphuric acid occur. That will be the same irrespective of which
halogen you are talking about. The total enthalpy change will be the sum of the enthalpy
changes for the halide ion half-reaction and the sulphuric acid half-reaction.
The table shows the energy changes which vary from halogen to halogen. We are
assuming that you start from solid sodiumhalide. The values for the lattice enthalpies for

other solid halides would be different, but the pattern will still be the same.
heat needed to
break up NaX
lattice
(kJ mol-1)

heat needed to
remove electron
from halide ion
(kJ mol-1)

heat released in
forming halogen
molecules
(kJ mol-1)

sum of
these
(kJ mol-1)

+902

+328

-79

+1151

Cl

+771

+349

-121

+999

Br

+733

+324

-112

+945

+684

+295

-107

+872

Note: There is likely to be some error in these figures. They come from a variety of
sources - some more reliable than others!

The overall enthalpy change for the halide half-reaction:


Look at the final column of figures.
Notice that the sum of these enthalpy changes gets less endothermic as you go down the
Group. That means that the total change (including the sulphuric acid) will become easier
as you go down the Group.
The amount of heat given out by the half-reaction involving the sulphuric acid must be
great enough to make the reactions with the bromide or iodide feasible, but not enough to
compensate for the more positive values produced by the fluoride and chloride halfreactions.
I don't know what the real value for the sulphuric acid half-reaction to produce sulphur
dioxide is, but it must be something like -980 kJ mol -1. Try the effect of combining that value
with the overall values in the table to see what happens to the total enthalpy change of
reaction for each halogen.

Exploring the changes in the various energy terms


Which individual energy terms in the table are most important in making the halogen halfreaction less endothermic as you go down the Group?
Chlorine to iodine
Considering the halogens from chlorine to iodine, it is the lattice enthalpy which has fallen
most. It falls by 87 kJ mol-1. By contrast, the heat needed to remove the electron has only
fallen by 54 kJ mol-1.
Both of these terms matter, but the fall in lattice enthalpy is the more important. This falls
because the ions are getting bigger. That means that they aren't as close to each other,
and so the attractions between positive and negative ions in the solid lattice get less.
The simplified explanation that we mentioned earlier concentrates on the less important fall
in the amount of energy needed to remove the electron from the ion. That's misleading!
Fluorine
Fluoride ions are very difficult to oxidise to fluorine. The table shows that this isn't anything
to do with the amount of energy needed to remove an electron from a fluoride ion. It is
actuallyeasier to remove an electron from a fluoride ion than from a chloride ion. In this
case, to make the generalisation that an electron gets easier to remove as the ion gets
bigger is just plain wrong!
Fluoride ions are so small that the electrons feel an abnormal amount of repulsion from
each other. This outweighs the effect of their closeness to the nucleus and makes them
easier to remove than you might expect.
There are two important reasons why fluoride ions are so difficult to oxidise.
The first is the comparatively very high lattice enthalpy of the solid fluoride. This is due to
the small size of the fluoride ion, which means that the positive and negative ions are very
close together and so strongly attracted to each other.
The other factor is the small amount of heat which is released when the fluorine atoms
combine to make fluorine molecules. (Scroll back and look at the table again.)

This is because of the low bond enthalpy of the F-F bond. The reason for this low bond
enthalpy is discusssed on a separate page.
Note: If you haven't read about this recently, you will find it on the page
about atomic and physical properties of the halogens

What if the halide ions were in solution rather than in a solid?


We have concentrated on the energetics of the process starting from solid halide ions
because that's what you use if you try to oxidise them using concentrated sulphuric acid.
What about oxidising them in solution using some different oxidising agent?
The trend is exactly the same. Fluoride ions are difficult to oxidise and it gets easier as you
go down the Group towards iodide ions. Looked at another way, fluoride ions aren't good
reducing agents, but iodide ions are.
The explanation this time has to start from the hydrated ions in solution rather than solid
ions. In a sense, this has already been done on another page.
Fluorine is a very powerful oxidising agent because it very readily forms its negative ion in
solution. That means that it will be energetically difficult to reverse the process.
By contrast, for the energetic reasons you will find discussed, iodine is relatively reluctant
to form its negative ion in solution. That means that it will be relatively easy to persuade it
to revert to iodine molecules again.
Note: You will find the oxidising ability of the halogensexplained in detail by
following this link.
Because you would now be thinking about the reverse of the processes described
on that page, you will have to reverse the sign of all the energy changes explored. If
I were you, I wouldn't bother to follow this up unless there is some overwhelming
reason to!

TESTING FOR HALIDE IONS


This page describes and explains the tests for halide ions (fluoride, chloride, bromide and
iodide) using silver nitrate solution followed by ammonia solution.

Using silver nitrate solution


Carrying out the test
This test has to be done in solution. If you start from a solid, it must first be dissolved in
pure water.
The solution is acidified by adding dilute nitric acid. (Remember: silver nitrate +
dilute nitric acid.) The nitric acid reacts with, and removes, other ions that might also give
a confusing precipitate with silver nitrate.
Silver nitrate solution is then added to give:
ion present

observation

F-

no precipitate

Cl-

white precipitate

Br-

very pale cream precipitate

I-

very pale yellow precipitate

The chloride, bromide and iodide precipitates are shown in the photograph:

The chloride precipitate is obviously white, but the other two aren't really very different from
each other. You couldn't be sure which you had unless you compared them side-by-side.
All of the precipitates change colour if they are exposed to light - taking on grey or purplish
tints.
The absence of a precipitate with fluoride ions doesn't prove anything unless you already
know that you must have a halogen present and are simply trying to find out which one. All
the absence of a precipitate shows is that you haven't got chloride, bromide or iodide ions
present.
The chemistry of the test
The precipitates are the insoluble silver halides - silver chloride, silver bromide or silver
iodide.

Silver fluoride is soluble, and so you don't get a precipitate.

Confirming the precipitate using ammonia solution

Carrying out the confirmation


Ammonia solution is added to the precipitates.
original precipitate

observation

AgCl

precipitate dissolves to give a colourless solution

AgBr

precipitate is almost unchanged using dilute ammonia solution,


but dissolves in concentrated ammonia solution to give a
colourless solution

AgI

precipitate is insoluble in ammonia solution of any concentration

Explaining what happens


Background
There is no such thing as an absolutely insoluble ionic compound. A precipitate will only
form if the concentrations of the ions in solution in water exceed a certain value - different
for every different compound.
This value can be quoted as a solubility product. For the silver halides, the solubility
product is given by the expression:
Ksp = [Ag+(aq)][X-(aq)]
The square brackets have their normal meaning, showing concentrations in mol dm -3.
If the actual concentrations of the ions in solution produce a value less than the solubility
product, you don't get a precipitate. If the product of the concentrations would exceed this
value, you do get a precipitate.
Essentially, the product of the ionic concentrations can never be greater than the solubility
product value. Enough of the solid is precipitated so that the ionic product is lowered to the

value of the solubility product.


Note: If your syllabus says that you need to know about
solubility product calculations, you might be interested in
mychemistry calculations book where they are explained
in detail.

Look at the way the solubility products vary from silver chloride to silver iodide. (You can't
quote a solubility product value for silver fluoride because it is too soluble. Solubility
products only work with compounds which are very, very sparingly soluble.)
Ksp
(mol2dm-6)
AgCl

1.8 x 10-10

AgBr

7.7 x 10-13

AgI

8.3 x 10-17
Note: These figures come from the Chemistry Data Book
by Stark and Wallace.

You can see that the compounds are all pretty insoluble, but become even less soluble as
you go from the chloride to the bromide to the iodide.
What is the ammonia doing?
The ammonia combines with silver ions to produce a complex ion called the
diamminesilver(I) ion, [Ag(NH3)2]+. This is a reversible reaction, but the complex is very
stable, and the position of equilibrium lies well to the right.

A solution in contact with one of the silver halide precipitates will contain a very small
concentration of dissolved silver ions. The effect of adding the ammonia is to lower this
concentration still further.
What happens if you multiply this new silver ion concentration by the halide ion
concentration? If the answer is less than the solubility product, the precipitate will dissolve.
That happens with the silver chloride, and with the silver bromide if concentrated ammonia
is used. The more concentrated ammonia tips the equilibrium even further to the right,
lowering the silver ion concentration even more.
The silver iodide is so insoluble that the ammonia won't lower the silver ion concentration
enough for the precipitate to dissolve.

An alternative test using concentrated sulphuric acid


If you add concentrated sulphuric acid to a solid sample of one of the halides you get these
results:
ion present

observation

F-

steamy acidic fumes (of HF)

Cl-

steamy acidic fumes (of HCl)

Br-

steamy acidic fumes (of HBr) contaminated with brown bromine


vapour

I-

Some steamy fumes (of HI), but lots of purple iodine vapour (plus
various red colours in the tube)
Note: The chemistry of this test is explained in detail on
another page.

The only possible confusion is between a fluoride and a chloride - they would behave
identically. You could distinguish between them by dissolving the original solid in water and
then testing with silver nitrate solution. The chloride gives a white precipitate; the fluoride
doesn't give a precipitate.
MANUFACTURING CHLORINE USING A DIAPHRAGM AND A MEMBRANE CELL

This page describes the manufacture of chlorine by the electrolysis of sodium chloride
solution using a diaphragm cell and a membrane cell. Both cells rely on the same
underlying chemistry, but differ in detail. For UK A level (or equivalent) purposes, you will
only need to know details of one of these cells. Read the background chemistry section
below, and then concentrate on the cell you need to know about.

Background chemistry
Chlorine is manufactured by electrolysing sodium chloride solution. In fact, the electrolysis
of sodium chloride solution can be used to make three useful substances - chlorine,
sodium hydroxide and hydrogen.

The chemistry of the electrolysis process


Sodium chloride solution contains:

sodium ions,

chloride ions,

hydrogen ions (from the water),

hydroxide ions (from the water).

The hydrogen and hydroxide ions come from the equilibrium:

Note: Strictly speaking, this is a simplification. The H+(aq)ions could be better shown
as hydroxonium ions, H3O+. That would need two water molecules on the left-hand
side of the equilibrium. The simplification is fine for this topic.

At any one time, the concentration of hydrogen ions or hydroxide ions will be very small the position of equilibrium lies well to the left-hand side.

At the anode
The negative ions, chloride and hydroxide, get attracted towards the positively charged
anode. It is actually easier to liberate hydroxide ions (to give oxygen) than chloride ions (to
give chlorine), but there are far, far more chloride ions arriving at the anode than hydroxide
ions.
The major reaction at the anode is therefore:

Two chloride ions each give up an electron to the anode, and the atoms produced combine
to give chlorine gas.
The chlorine is, however, contaminated with small amounts of oxygen because of a
reaction involving hydroxide ions giving up electrons as well.

The chlorine has to be purified to remove this oxygen.

At the cathode
Sodium ions and hydrogen ions (from the water) are attracted to the negative cathode. It is
much easier for a hydrogen ion to pick up an electron than for a sodium ion. So this
reaction happens:

As the hydrogen ions are converted into hydrogen gas, the water equilibrium tips to the
right to replace them.

The net effect of this is that there is a build up of sodium ions and these newly-produced
hydroxide ions around the cathode. In other words, sodium hydroxide solution is being
formed around the cathode.

The need to keep all the products separate


If chlorine comes into contact with hydrogen, it produces a mixture which will explode
violently on exposure to sunlight or heat. Hydrogen chloride gas would be produced.
Obviously, the two gases need to be kept apart.
However, chlorine also reacts with sodium hydroxide solution to produce a mixture of
sodium chloride and sodium chlorate(I) - also known as sodium hypochlorite. This mixture
is commonly sold as bleach.

Therefore, if you are trying to manufacture chlorine and sodium hydroxide rather than
bleach, you have to keep the chlorine and sodium hydroxide apart as well.
The diaphragm and membrane cells are designed so that all the products are kept
separate.

The diaphragm cell

Note: This is a simplification of a real cell. For example, in a real diaphragm cell, the
electrodes are not a single block of metal. If you are interested, you can find pictures
and descriptions of real electrodes by doing a Google search ondiaphragm cell and
looking for manufacturers' websites.

The diaphragm
The diaphragm is made of a porous mixture of asbestos and polymers. The solution can
seep through it from the anode compartment into the cathode side.
Notice that there is a higher level of liquid on the anode side. That makes sure that the flow

of liquid is always from left to right - preventing any of the sodium hydroxide solution
formed finding its way back to where chlorine is being produced.

Production of the chlorine


Chlorine is produced at the titanium anode according to the equation:

It is contaminated with some oxygen because of the reaction:

The chlorine is purified by liquifying it under pressure. The oxygen stays as a gas when it is
compressed at ordinary temperatures.

Production of the hydrogen


The hydrogen is produced at the steel cathode:

Production of the sodium hydroxide


A dilute solution of sodium hydroxide solution is also produced at the cathode (see above
for the explanation of what happens at the cathode). It is highly contaminated with
unchanged sodium chloride solution.
The sodium hydroxide solution leaving the cell is concentrated by evaporation. During this
process, most of the sodium chloride crystallises out as solid salt. The salt can be
separated, dissolved in water, and passed through the cell again.
Even after concentration, the sodium hydroxide will still contain a small percentage of
sodium chloride.

The membrane cell

Note: This is a simplification of a real cell to show the main features. You will find
other diagrams with the inlets and outlets in different places or in more detail. This
isn't something you need to worry about at this level.

The membrane
The membrane is made from a polymer which only allows positive ions to pass through it.
That means that the only the sodium ions from the sodium chloride solution can pass
through the membrane - and not the chloride ions.
The advantage of this is that the sodium hydroxide solution being formed in the right-hand
compartment never gets contaminated with any sodium chloride solution.
The sodium chloride solution being used has to be pure. If it contained any other metal
ions, these would also pass through the membrane and so contaminate the sodium
hydroxide solution.

Production of the chlorine


Chlorine is produced at the titanium anode according to the equation:

It is contaminated with some oxygen because of the reaction:

The chlorine is purified by liquifying it under pressure. The oxygen stays as a gas when it is
compressed at ordinary temperatures.

Production of the hydrogen


The hydrogen is produced at the nickel cathode:

Production of the sodium hydroxide


An approximately 30% solution of sodium hydroxide solution is also produced at the
cathode (see above - in the background chemistry section - for the explanation of what
happens at the cathode).
THE GENERAL FEATURES OF TRANSITION METAL CHEMISTRY

This page explains what a transition metal is in terms of its electronic structure, and
then goes on to look at the general features of transition metal chemistry. These
include variable oxidation state (oxidation number), complex ion formation, coloured
ions, and catalytic activity.
You will find some of this covered quite briefly on this page with links to other parts

of the site where the topics are covered in more detail.

The electronic structures of transition metals


What is a transition metal?
The terms transition metal (or element) and d block element are sometimes used as
if they mean the same thing. They don't - there's a subtle difference between the two
terms.
We'll explore d block elements first:
d block elements
You will remember that when you are building the Periodic Table and working out
where to put the electrons using the Aufbau Principle, something odd happens after
argon.
At argon, the 3s and 3p levels are full, but rather than fill up the 3d levels next, the 4s
level fills instead to give potassium and then calcium.
Only after that do the 3d levels fill.
Note: If you aren't sure about atomic orbitals and electronic structures, you really need to follow
this link before you go on. It takes you to a page explaining atomic orbitals and then on to other
pages about electronic structures.
If you do follow the link, use the BACK button on your browser (or the History file or Go menu) to
return quickly to this page.

The elements in the Periodic Table which correspond to the d levels filling are called d
block elements. The first row of these is shown in the shortened form of the Periodic
Table below.

The electronic structures of the d block elements shown are:


Sc

[Ar] 3d14s2

Ti

[Ar] 3d24s2

[Ar] 3d34s2

Cr

[Ar] 3d54s1

Mn

[Ar] 3d54s2

Fe

[Ar] 3d64s2

Co

[Ar] 3d74s2

Ni

[Ar] 3d84s2

Cu

[Ar] 3d104s1

Zn

[Ar] 3d104s2

You will notice that the pattern of filling isn't entirely tidy! It is broken at both chromium and
copper.
Note: This is something that you are just going to have to accept. There is
no simple explanation for it which is usable at this level. Any simple explanation which is given is

faulty!
People sometimes say that a half-filled d level as in chromium (with one electron in each orbital)
is stable, and so it is - sometimes! But you then have to look at why it is stable. The obvious
explanation is that chromium takes up this structure because separating the electrons minimises
the repulsions between them - otherwise it would take up some quite different structure.
But you only have to look at the electronic configuration of tungsten (W) to see that this
apparently simple explanation doesn't always work. Tungsten has the same number of outer
electrons as chromium, but its outer structure is different - 5d46s2. Again the electron repulsions
must be minimised - otherwise it wouldn't take up this configuration. But in this case, it isn't true
that the half-filled state is the most stable - it doesn't seem very reasonable, but it's a fact! The
real explanation is going to be much more difficult than it seems at first sight.
Neither can you use the statement that a full d level (for example, in the copper case) is stable,
unless you can come up with a proper explanation of why that is. You can't assume that looking
nice and tidy is a good enough reason!
If you can't explain something properly, it is much better just to accept it than to make up faulty
explanations which sound OK on the surface but don't stand up to scrutiny!

Transition metals
Not all d block elements count as transition metals! There are discrepancies between the
various UK-based syllabuses, but the majority use the definition:
A transition metal is one which forms one or more stable ions which have incompletely
filled d orbitals.
Note: The most recent IUPAC definition includes the possibility of the element itself having
incomplete d orbitals as well. This is unlikely to be a big problem (it only really arises with
scandium), but it would pay you to learn the version your syllabus wants. Both versions of the
definition are currently in use in various UK-based syllabuses.
If you are working towards a UK-based exam and haven't got a copy of your syllabus, follow this
link to find out how to get one. Use the BACK button on your browser to return quickly to this
page.

On the basis of the definition outlined above, scandium and zinc don't count as transition
metals - even though they are members of the d block.
Scandium has the electronic structure [Ar] 3d14s2. When it forms ions, it always loses the 3
outer electrons and ends up with an argon structure. The Sc 3+ ion has no d electrons and
so doesn't meet the definition.
Zinc has the electronic structure [Ar] 3d104s2. When it forms ions, it always loses the two 4s
electrons to give a 2+ ion with the electronic structure [Ar] 3d 10. The zinc ion has full d
levelsand doesn't meet the definition either.
By contrast, copper, [Ar] 3d104s1, forms two ions. In the Cu+ ion the electronic structure is
[Ar] 3d10. However, the more common Cu2+ ion has the structure [Ar] 3d9.
Copper is definitely a transition metal because the Cu 2+ ion has an incomplete d level.

Transition metal ions


Here you are faced with one of the most irritating facts in chemistry at this level! When you
work out the electronic structures of the first transition series (from scandium to zinc) using
the Aufbau Principle, you do it on the basis that the 3d orbitals have a higher energy than
the 4s orbital.
That means that you work on the assumption that the 3d electrons are added after the 4s
ones.
However, in all the chemistry of the transition elements, the 4s orbital behaves as the
outermost, highest energy orbital. When these metals form ions, the 4s electrons are
always lost first.
You must remember this:
When d-block elements form ions, the 4s electrons are lost first.
Note: The problem here is that the Aufbau Principle can only really be used as a way

of working out the electronic structures of most atoms. It is a simple way of doing that, although
it fails with some, like chromium or copper, of course, and you have to learn these.
There is, however, a flaw in the theory behind it which produces problems like this. Why are the
apparently higher energy 3d electrons not the ones to get lost when the metal ionises?
I have written a detailed explanation of this on another page called the order of filling 3d and 4s
orbitals. If you are a teacher or a very confident student then you might like to follow this link.
If you aren't so confident, I suggest that you ignore it. Make sure that you can work out the
structures of these atoms using the Aufbau Principle on the assumption that the 3d orbitals fill
after the 4s, and learn that when the atoms ionise, the 4s electrons are always lost first. Just
ignore the contradictions between these two ideas!

To write the electronic structure for Co2+:


Co

[Ar] 3d74s2

Co2+

[Ar] 3d7

The 2+ ion is formed by the loss of the two 4s electrons.


To write the electronic structure for V3+:
V

[Ar] 3d34s2

V3+

[Ar] 3d2

The 4s electrons are lost first followed by one of the 3d electrons.


Note: You will find more examples of writing the electronic structures for d block ions, by
following this link.
Use the BACK button on your browser to return quickly to this page.

Variable oxidation state (number)


One of the key features of transition metal chemistry is the wide range of oxidation states
(oxidation numbers) that the metals can show.
Note: If you aren't sure about oxidation states, you really need to follow this link before you go
on.
Use the BACK button on your browser to return quickly to this page.

It would be wrong, though, to give the impression that onlytransition metals can have
variable oxidation states. For example, elements like sulphur or nitrogen or chlorine have a
very wide range of oxidation states in their compounds - and these obviously aren't
transition metals.
However, this variability is less common in metals apart from the transition elements. Of
the familiar metals from the main groups of the Periodic Table, only lead and tin show
variable oxidation state to any extent.
Examples of variable oxidation states in the transition metals
Iron
Iron has two common oxidation states (+2 and +3) in, for example, Fe 2+ and Fe3+. It also
has a less common +6 oxidation state in the ferrate(VI) ion, FeO 42-.
Manganese
Manganese has a very wide range of oxidation states in its compounds. For example:
+2

in Mn2+

+3

in Mn2O3

+4

in MnO2

+6

in MnO42-

+7

in MnO4-

Other examples
You will find the above examples and others looked at in detail if you explore the chemistry
of individual metals from the transition metal menu. There is a link to this menu at the
bottom of the page.

Explaining the variable oxidation states in the transition metals


We'll look at the formation of simple ions like Fe 2+ and Fe3+.
When a metal forms an ionic compound, the formula of the compound produced depends
on the energetics of the process. On the whole, the compound formed is the one in which
most energy is released. The more energy released, the more stable the compound.
There are several energy terms to think about, but the key ones are:

The amount of energy needed to ionise the metal (the sum of the various ionisation
energies)

The amount of energy released when the compound forms. This will either be lattice
enthalpy if you are thinking about solids, or the hydration enthalpies of the ions if
you are thinking about solutions.

The more highly charged the ion, the more electrons you have to remove and the more
ionisation energy you will have to provide.
But off-setting this, the more highly charged the ion, the more energy is released either as
lattice enthalpy or the hydration enthalpy of the metal ion.
Note: What I am talking about here in a general way are Born-Haber cycles. You will find these

covered in theenergetics section of Chemguide, or my chemistry calculations book.

Thinking about a typical non-transition metal (calcium)


Calcium chloride is CaCl2. Why is that?
If you tried to make CaCl, (containing a Ca + ion), the overall process is slightly exothermic.
By making a Ca2+ ion instead, you have to supply more ionisation energy, but you get out
lots more lattice energy. There is much more attraction between chloride ions and
Ca2+ ions than there is if you only have a 1+ ion. The overall process is very exothermic.
Because the formation of CaCl2 releases much more energy than making CaCl, then
CaCl2 is more stable - and so forms instead.
What about CaCl3? This time you have to remove yet another electron from calcium.
The first two come from the 4s level. The third one comes from the 3p. That is much closer
to the nucleus and therefore much more difficult to remove. There is a large jump in
ionisation energy between the second and third electron removed.
Although there will be a gain in lattice enthalpy, it isn't anything like enough to compensate
for the extra ionisation energy, and the overall process is very endothermic.
It definitely isn't energetically sensible to make CaCl 3!
Thinking about a typical transition metal (iron)
Here are the changes in the electronic structure of iron to make the 2+ or the 3+ ion.
Fe

[Ar] 3d64s2

Fe2+

[Ar] 3d6

Fe3+

[Ar] 3d5

The 4s orbital and the 3d orbitals have very similar energies. There isn't a huge jump in the

amount of energy you need to remove the third electron compared with the first and
second.
The figures for the first three ionisation energies (in kJ mol -1) for iron compared with those
of calcium are:
metal

1st IE

2nd IE

3rd IE

Ca

590

1150

4940

Fe

762

1560

2960

There is an increase in ionisation energy as you take more electrons off an atom because
you have the same number of protons attracting fewer electrons. However, there is much
less increase when you take the third electron from iron than from calcium.
In the iron case, the extra ionisation energy is compensated more or less by the extra
lattice enthalpy or hydration enthalpy evolved when the 3+ compound is made.
The net effect of all this is that the overall enthalpy change isn't vastly different whether you
make, say, FeCl2 or FeCl3. That means that it isn't too difficult to convert between the two
compounds.

The formation of complex ions


What is a complex ion?
A complex ion has a metal ion at its centre with a number of other molecules or ions
surrounding it. These can be considered to be attached to the central ion by co-ordinate
(dative covalent) bonds. (In some cases, the bonding is actually more complicated than
that.)
The molecules or ions surrounding the central metal ion are called ligands.

Simple ligands include water, ammonia and chloride ions.

What all these have got in common is active lone pairs of electrons in the outer energy
level. These are used to form co-ordinate bonds with the metal ion.
Some examples of complex ions formed by transition metals
[Fe(H2O)6]2+
[Co(NH3)6]2+
[Cr(OH)6]3[CuCl4]2Other metals also form complex ions - it isn't something that onlytransition metals do.
Transition metals do, however, form a very wide range of complex ions.
Note: You will find much more about complex ions by following this link. It will take you to a part
of the site dealing exclusively with complex ions.
If you do follow the link, use the BACK button on your browser (or the History file or Go menu) if
you want to return to this page again.

The formation of coloured compounds


Some common examples
The diagrams show aproximate colours for some common transition metal complex ions.

You will find these and others discussed if you follow links to individual metals from the
transition metal menu (link at the bottom of the page).
Alternatively, you could explore the complex ions menu (follow the link in the help box
which has just disappeared off the top of the screen).
The origin of colour in the transition metal ions
When white light passes through a solution of one of these ions, or is reflected off it, some
colours in the light are absorbed. The colour you see is how your eye perceives what is
left.
Attaching ligands to a metal ion has an effect on the energies of the d orbitals. Light is
absorbed as electrons move between one d orbital and another. This is explained in detail
on another page.
Note: You will find a detailed explanation of the origin of colour in complex ions and the factors
which cause it to change by following this link. That page is on the part of the site dealing with
complex ions.

Use the BACK button on your browser if you want to return to this page again.

Catalytic activity
Transition metals and their compounds are often good catalysts. A few of the more obvious
cases are mentioned below, but you will find catalysis explored in detail elsewhere on the
site (follow the link after the examples).
Transition metals and their compounds function as catalysts either because of their ability
to change oxidation state or, in the case of the metals, to adsorb other substances on to
their surface and activate them in the process. All this is expored in the main catalysis
section.
Transition metals as catalysts
Iron in the Haber Process
The Haber Process combines hydrogen and nitrogen to make ammonia using an iron
catalyst.

Nickel in the hydrogenation of C=C bonds


This reaction is at the heart of the manufacture of margarine from vegetable oils.
However, the simplest example is the reaction between ethene and hydrogen in the
presence of a nickel catalyst.

Transition metal compounds as catalysts

Vanadium(V) oxide in the Contact Process


At the heart of the Contact Process is a reaction which converts sulphur dioxide into
sulphur trioxide. Sulphur dioxide gas is passed together with air (as a source of oxygen)
over a solid vanadium(V) oxide catalyst.

Iron ions in the reaction between persulphate ions and iodide ions
Persulphate ions (peroxodisulphate ions), S 2O82-, are very powerful oxidising agents. Iodide
ions are very easily oxidised to iodine. And yet the reaction between them in solution in
water is very slow.
The reaction is catalysed by the presence of either iron(II) or iron(III) ions.

Note: You will find detailed explanations of these reactions in the catalysis section of the site.
You could usefully start with the types of catalysts page.
Use the BACK button on your browser to return quickly to this page.

VANADIUM
This page looks at some aspects of vanadium chemistry required for UK A' level exams.
That includes the use of vanadium(V) oxide as a catalyst in the Contact Process, and
converting between the various vanadium oxidation states.

Vanadium(V) oxide as a catalyst in the Contact Process


The overall reaction

During the Contact Process for manufacturing sulphuric acid, sulphur dioxide has to be
converted into sulphur trioxide. This is done by passing sulphur dioxide and oxygen over a
solid vanadium(V) oxide catalyst.

Note: The equation is written with the half in it to make the explanation below tidier. You
may well be familiar with the equation written as twice that shown, but the present version is
perfectly acceptable. It is also shown as a one-way rather than a reversible reaction to
avoid complicating things.

How the reaction works


This is a good example of the ability of transition metals and their compounds to act as
catalysts because of their ability to change their oxidation state (oxidation number).
Note: If you aren't sure about oxidation states, you really ought to follow this link before
you go on. You will need to be confident about oxidation states throughout the whole of the
present page.
Use the BACK button on your browser to return to this page.

The sulphur dioxide is oxidised to sulphur trioxide by the vanadium(V) oxide. In the
process, the vanadium(V) oxide is reduced to vanadium(IV) oxide.

The vanadium(IV) oxide is then re-oxidised by the oxygen.

Although the catalyst has been temporarily changed during the reaction, at the end it is
chemically the same as it started.

Note: If you want more detail about the Contact Process, you will find a full description of
the conditions used and the reasons for them by following this link.
If you want to find out more about catalysis, this link will take you to an introductory page
about catalysts with further links to other catalysis pages if you want them.
Use the BACK button on your browser (or the History file of Go menu) if you want to return
to this page later.

Vanadium's oxidation states


Vanadium has oxidation states in its compounds of +5, +4, +3 and +2. This section looks at
ways of changing between them. It starts with a bit of description, and then goes on to look
at the reactions in terms of standard redox potentials (standard electrode potentials).
Observing the changes in the lab
Reducing vanadium(V) in stages to vanadium(II)
The usual source of vanadium in the +5 oxidation state is ammonium metavanadate,
NH4VO3. This isn't very soluble in water and is usually first dissolved in sodium hydroxide
solution.
The solution can be reduced using zinc and an acid - either hydrochloric acid or sulphuric
acid, usually using moderately concentrated acid.
The exact vanadium ion present in the solution is very complicated, and varies with the pH
of the solution. The reaction is done under acidic conditions when the main ion present
isVO2+ - called the dioxovanadium(V) ion.
Note: The ion is usually written as VO2+, but is more accurately [VO2(H2O)4]+.

If you do the reaction in a small flask, it is normally stoppered with some cotton wool. This
allows hydrogen (produced from a side reaction between the zinc and acid) to escape. At

the same time it stops much air from entering. This prevents re-oxidation of the lower
oxidation states of vanadium (particularly the +2 state) by oxygen in the air.
The reaction is usually warmed so that the changes happen in a reasonable time.
The reduction is shown in two stages. Some individual important colours are shown, but
the process is one continuous change from start to finish.
The reduction from +5 to +4

It is important to notice that the green colour you see isn't actually another oxidation state.
it is just a mixture of the original yellow of the +5 state and the blue of the +4.
Be very careful with the formulae of the two vanadium ions - they are very easy to confuse!
Note: Just like the VO2+ ion, the VO2+ ion will have water molecules attached to it as well [VO(H2O)5]2+. We usually use the simpler form.

The reduction from +4 to +2


The colour changes just continue.

The reason for the inverted commas around the vanadium(III) ion is that this is almost
certainly a simplification. The exact nature of the complex ion will depend on which acid
you use in the reduction process. The simplification is probably reasonable at this level.
Note: If you use hydrochloric acid, you get a ligand exchange reaction to give
[V(H2O)4Cl2]+. This causes the green colour in the vanadium(III) solution.
I am uncertain about the sulphuric acid case. One source says that with sulphuric acid, you
actually get the [V(H2O)6]3+ ion which is a dull grey-blue colour. However, when I checked
this in the lab before writing this, I gotexactly the same green colour with both acids.
One possibility is that you get another ligand exchange reaction with sulphate ions to give
[V(H2O)5(SO4)]+, but I haven't been able to confirm this.
There is, however, a very similar case in chromium chemistry which is discussed on the
page about ligand exchange reactions.
If you follow this link, use the BACK button on your browser to return to this page.

Re-oxidation of the vanadium(II)


The vanadium(II) ion is very easily oxidised. If you remove the cotton wool from the flask
and pour some solution into a test tube, it turns green because of its contact with oxygen in
the air. It is oxidised back to vanadium(III).
Note: It only changes this quickly if the solution is still warm. In the cold, the change is
quite a lot slower.

If it is allowed to stand for a long time, the solution eventually turns blue as the air oxidises
it back to the vanadium(IV) state - VO2+ ions.
Adding nitric acid (a reasonably powerful oxidising agent) to the original vanadium(II)
solution also produces blue VO2+ ions. The vanadium(II) is again oxidised back to
vanadium(IV).

Important! There is no point in reading the rest of this page unless you are familiar
with redox potentials (electrode potentials).
This link will take you to a page explaining how to use redox potentials in the present
context. However, you should be aware that it is the final page in a linked sequence. That
page will give you the opportunity to start at the beginning if you need to. You would be
strongly advised to do that unless you are really confident! It will take you some time, but at
the end you should really understand how to use redox potentials.
If you think you know about E values, it would probably be quicker to read the rest of this
current page and then come back to this link if you need to.
If you follow this link, use the BACK button on your browser (or the History file or the Go
menu) to return quickly to this page.

Explaining the changes in terms of redox potentials (electrode potentials)


Using zinc as the reducing agent
The first stage of the series of reductions
Let's look at the first stage of the reduction - from VO 2+ to VO2+. The redox potential for the
vanadium half-reaction is given by:

The corresponding equilibrium for the zinc is:

The simple principle is that if you couple two of these half-reactions together, the one
with the more positive E value will move to the right; the one with the more negative (or
less positive) E moves to the left.
Note: If you have learnt to use E values using some more complicated method (and there
are lots of unnecessarily complicated methods around!), it would pay you to follow the link
above to find out how to do it all much more easily.

So . . . if you mix together zinc and VO2+ ions in the presence of acid to provide the H + ions:

That converts the two equilibria into two one-way reactions. You can write these down and
combine them to give the ionic equation for the reaction if you want to.

Note: If you aren't happy about building up ionic equationslike this, you could usefully
follow this link.
Use the BACK button on your browser to return quickly to this page.

The other stages of the reaction


Here are the E values for all the steps of the reduction from vanadium(V) to vanadium(II):

. . . and here is the zinc value again:

Remember that for the vanadium reactions to move to the right (which is what we want),
their E values must be more positive than whatever you are reacting them with.
In other words, for the reactions to work, zinc must always have the more negative value and that's the case.
Zinc can reduce the vanadium through each of these steps to give the vanadium(II) ion.
Using other reducing agents
Suppose you replaced zinc as the reducing agent by tin. How far would the set of
reductions go this time?
Here are the E values again:

. . . and here is the tin value:

In order for each reduction to happen, the vanadium reaction has to have the more positive
E value because we want it to go to the right. That means that the tin must have the more
negative value.
In the first vanadium equation (from +5 to +4), the tin value is more negative. That works
OK.
In the second vanadium equation (from +4 to +3), the tin value is again the more negative.
That works as well.
But in the final vanadium reaction (from +3 to +2), tin no longer has the more negative E
value. Tin won't reduce vanadium(III) to vanadium(II).
Important! If this doesn't seem pretty obvious to you, then you don't really understand
about redox potentials.
This link will take you to the redox potential menu. Spend some time by starting at the
beginning of the sequence of pages you will find there.
If you follow this link, use the BACK button on your browser (or the History file or the Go
menu) if you want to return to this page later.

Re-oxidation of the vanadium(II)


The vanadium(II) oxidation state is easily oxidised back to vanadium(III) - or even higher.

Oxidation by hydrogen ions


You will remember that the original reduction we talked about was carried out using zinc
and an acid in a flask stoppered with a piece of cotton wool to keep the air out. Air will
rapidly oxidise the vanadium(II) ions - but so also will the hydrogen ions present in the
solution!
The vanadium(II) solution is only stable as long as you keep the air out, and in the
presence of the zinc. The zinc is necessary to keep the vanadium reduced.
What happens if the zinc isn't there? Look at these E values:

The reaction with the more negative E value goes to the left; the reaction with the more
positive (or less negative) one to the right.
That means that the vanadium(II) ions will be oxidised to vanadium(III) ions, and the
hydrogen ions reduced to hydrogen.
Will the oxidation go any further - for example, to the vanadium(IV) state?
Have a look at the E values and decide:

In order for the vanadium equilibrium to move to the left, it would have to have the more
negative E value. It hasn't got the more negative E value and so the reaction doesn't
happen.
Oxidation by nitric acid
In a similar sort of way, you can work out how far nitric acid will oxidise the vanadium(II).
Here's the first step:

The vanadium reaction has the more negative E value and so will move to the left; the
nitric acid reaction moves to the right.
Nitric acid will oxidise vanadium(II) to vanadium(III).
The second stage involves these E values:

The nitric acid again has the more positive E value and so moves to the right. The more
negative (less positive) vanadium reaction moves to the left.
Nitric acid will certainly oxidise vanadium(III) to vanadium(IV).
Will it go all the way to vanadium(V)?

No, it won't! For the vanadium reaction to move to the left to form the dioxovanadium(V)
ion, it would have to have the more negative (less positive) E value. It hasn't got a less
positive value, and so the reaction doesn't happen.
Note: There are several possible half-reactions involving the nitric acid with a variety of E
values. Two of these actually have E values more positive than +1.00 and so, in principle,
nitric acid could seem to be able to oxidise vanadium(IV) to vanadium(V) - but involving
different products from the nitric acid.
In practice, if you do this reaction in the lab, the solution turns blue - producing the
vanadium(IV) state. Just because the E values tell you that a reaction is possible, you can't
assume that it will actually happen. There may be very large activation energy barriers
involved, causing the reaction to be infinitely slow!

You can work out the effect of any other oxidising agent on the lower oxidation states of
vanadium in exactly the same way. But don't assume that because the E values show that
a reaction ispossible, it will necessarily happen.

CHROMIUM

This page looks at some aspects of chromium chemistry required for UK A level (and its
equivalents). It includes: reactions of chromium(III) ions in solution (summarised from
elsewhere on the site); the interconversion of the various oxidation states of chromium; the
chromate(VI)-dichromate(VI) equilibrium; and the use of dichromate(VI) ions as an
oxidising agent (including titrations).
The first part of this page is a summary of the reactions of chromium(III) ions in solution.
You will find links to other pages where these reactions are discussed in more detail.
You are very unlikely to need everything on this page. Check your syllabus and past
papers to find out exactly what you need to know.

Reactions of chromium(III) ions in solution


The simplest ion that chromium forms in solution is the hexaaquachromium(III) ion [Cr(H2O)6]3+.
Note: If you aren't happy about complex ions (including the way they are bonded and named), it would
pay you to follow this link and explore the first couple of pages in the complex ions menu before you go
on.
Use the BACK button on your browser to return to this page.

The acidity of the hexaaqua ions


In common with the other 3+ ions, the hexaaquachromium(III) ion is fairly acidic - with a pH
for typical solutions in the 2 - 3 range.
The ion reacts with water molecules in the solution. A hydrogen ion is lost from one of the
ligand water molecules:

The complex ion is acting as an acid by donating a hydrogen ion to water molecules in the
solution. The water is, of course, acting as a base by accepting the hydrogen ion.
Because of the confusing presence of water from two different sources (the ligands and the
solution), it is easier to simplify this:

However, if you write it like this, remember that the hydrogen ion isn't just falling off the
complex ion. It is being pulled off by a water molecule in the solution. Whenever you write
"H+(aq)" what you really mean is a hydroxonium ion, H3O+.
Note: You will find the full reasons for the acidity of hexaaqua ions if you follow this link. You only need
to read the beginning of that page which concentrates on explaining the acidity of the hexaaquairon(III)
ion. What is said applies equally to the chromium-containing ion.
Use the BACK button on your browser to return to this page.

Ligand exchange reactions involving chloride or sulphate ions


The hexaaquachromium(III) ion is a "difficult to describe" violet-blue-grey colour. However,
when it is produced during a reaction in a test tube, it is often green.
We nearly always describe the green ion as being Cr 3+(aq) - implying the

hexaaquachromium(III) ion. That's actually an over-simplification.


What happens is that one or more of the ligand water molecules get replaced by a negative
ion in the solution - typically sulphate or chloride.
Replacement of the water by sulphate ions
You can do this simply by warming some chromium(III) sulphate solution.

One of the water molecules is replaced by a sulphate ion. Notice the change in the charge
on the ion. Two of the positive charges are cancelled by the presence of the two negative
charges on the sulphate ion.
Replacement of the water by chloride ions
In the presence of chloride ions (for example with chromium(III) chloride), the most
commonly observed colour is green. This happens when two of the water molecules are
replaced by chloride ions to give the tetraaquadichlorochromium(III) ion - [Cr(H 2O)4Cl2]+.
Once again, notice that replacing water molecules by chloride ions changes the charge on
the ion.
Note: You will find an extensive discussion of ligand exchange reactions if you follow this link.
Use the BACK button on your browser to return to this page.

Reactions of hexaaquachromium(III) ions with hydroxide ions

Hydroxide ions (from, say, sodium hydroxide solution) remove hydrogen ions from the
water ligands attached to the chromium ion.
Once a hydrogen ion has been removed from three of the water molecules, you are left
with a complex with no charge - a neutral complex. This is insoluble in water and a
precipitate is formed.

Note: The colour coding is to show that this isn't a ligand exchange reaction. The oxygens which were
originally attached to the chromium are still attached in the neutral complex.

But the process doesn't stop there. More hydrogen ions are removed to give ions like
[Cr(H2O)2(OH)4]- and [Cr(OH)6]3-.
For example:

The precipitate redissolves because these ions are soluble in water.


In the test-tube, the colour changes are:

Note: You will find the reactions between hexaaqua ions and hydroxide ions discussed in detail if you
follow this link.
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Reactions of hexaaquachromium(III) ions with ammonia solution


The ammonia acts as both a base and a ligand. With a small amount of ammonia,
hydrogen ions are pulled off the hexaaqua ion exactly as in the hydroxide ion case to give
the same neutral complex.

That precipitate dissolves to some extent if you add an excess of ammonia (especially if it
is concentrated). The ammonia replaces water as a ligand to give
hexaamminechromium(III) ions.

Note: You might wonder why this second equation is given starting from the original hexaaqua ion rather
than the neutral complex. Explaining why the precipitate redissolves is quite complicated. You will find the
explanation in full (although by reference to the corresponding copper case) on the page about
thereactions between hexaaqua ions and ammonia solution.
Use the BACK button on your browser to return to this page.

The colour changes are:

Reactions of hexaaquachromium(III) ions with carbonate ions


If you add sodium carbonate solution to a solution of hexaaquachromium(III) ions, you get
exactly the same precipitate as if you added sodium hydroxide solution or ammonia
solution.
This time, it is the carbonate ions which remove hydrogen ions from the hexaaqua ion and
produce the neutral complex.
Depending on the proportions of carbonate ions to hexaaqua ions, you will get either
hydrogencarbonate ions formed or carbon dioxide gas from the reaction between the
hydrogen ions and carbonate ions. The more usually quoted equation shows the formation
of carbon dioxide.

Apart from the carbon dioxide, there is nothing new in this reaction:

Note: You will find the reactions between hexaaqua ions and carbonate ions discussed in detail if you
follow this link.
Use the BACK button on your browser to return to this page.

The oxidation of chromium(III) to chromium(VI)


An excess of sodium hydroxide solution is added to a solution of the
hexaaquachromium(III) ions to produce a solution of green hexahydroxochromate(III) ions.

This is then oxidised by warming it with hydrogen peroxide solution. You eventually get a
bright yellow solution containing chromate(VI) ions.

The equation for the oxidation stage is:

Note: Although it is still a complex ion, you don't write square brackets around the chromate(VI) ion - any
more than you would around a sulphate or carbonate ion.
If you want to know how to work out this equation , follow this link.
Use the BACK button on your browser to return to this page.

Some chromium(VI) chemistry


The chromate(VI)-dichromate(VI) equilibrium
You are probably more familiar with the orange dichromate(VI) ion, Cr 2O72-, than the yellow

chromate(VI) ion, CrO42-.


Changing between them is easy:
If you add dilute sulphuric acid to the yellow solution it turns orange. If you add sodium
hydroxide solution to the orange solution it turns yellow.

Note: If you had just produced the yellow chromate(VI) ions by oxidising chromium(III) ions using
hydrogen peroxide, you can't convert them into dichromate(VI) ions without taking a precaution first.
In the presence of acid, dichromate(VI) ions react with any hydrogen peroxide which is left in the solution
from the original reaction. To prevent this, you heat the solution for some time to decompose the
hydrogen peroxide into water and oxygen before adding the acid.

The equilibrium reaction at the heart of the interconversion is:

If you add extra hydrogen ions to this, the equilibrium shifts to the right. This is consistent
with Le Chatelier's Principle.

Note: If you aren't familiar with Le Chatelier's Principle, you should follow this link and read the first part

of that page about the effect of concentration on position of equilibrium.


Use the BACK button on your browser to return to this page.

If you add hydroxide ions, these react with the hydrogen ions. The equilibrium tips to the
left to replace them.

Making potassium dichromate(VI) crystals


Potassium dichromate crystals can be made by a combination of the reactions we've
already looked at on this page.
Starting from a source of chromium(III) ions such as chromium(III) chloride solution:
You add potassium hydroxide solution to give first a grey-green precipitate and then the
dark green solution containing [Cr(OH)6]3-ions. This is all described in detail further up the
page. Notice that you have to use potassium hydroxide. If you used sodium hydroxide, you
would end up eventually with sodium dichromate(VI).
Now you oxidise this solution by warming it with hydrogen peroxide solution. The solution
turns yellow as potassium chromate(VI) is formed. This reaction is also described further
up the page.
All that is left is to convert the yellow potassium chromate(VI) solution into orange
potassium dichromate(VI) solution. You may remember that that is done by adding acid.

This is described above if you have forgotten.


Unfortunately there is a problem here. Potassium dichromate will react with any excess
hydrogen peroxide to give initially an unstable deep blue solution and it eventually gives
the original chromium(III) ions again! To get around this, you first need to destroy any
excess hydrogen peroxide.
This is done by boiling the solution. Hydrogen peroxide decomposes on heating to give
water and oxygen. The solution is boiled until no more bubbles of oxygen are produced.
The solution is heated further to concentrate it, and then concentrated ethanoic acid is
added to acidify it. Orange crystals of potassium dichromate are formed on cooling.

The reduction of dichromate(VI) ions with zinc and an acid


Dichromate(VI) ions (for example, in potassium dichromate(VI) solution) can be reduced to
chromium(III) ions and then to chromium(II) ions using zinc and either dilute sulphuric acid
or hydrochloric acid.
Hydrogen is produced from a side reaction between the zinc and acid. This must be
allowed to escape, but you need to keep air out of the reaction. Oxygen in the air rapidly
re-oxidises chromium(II) to chromium(III).
An easy way of doing this is to put a bit of cotton wool in the top of the flask (or test-tube)
that you are using. This allows the hydrogen to escape, but stops most of the air getting in
against the flow of the hydrogen.

The reason for the inverted commas around the chromium(III) ion is that this is a
simplification. The exact nature of the complex ion will depend on which acid you use in the
reduction process. This has already been discussed towards the top of the page.
Note: To re-read this use this link.

The equations for the two stages of the reaction are:


For the reduction from +6 to +3:

For the reduction from +3 to +2:

Note: If you don't know how to work out equations like this, you can find out how to do it on the page
about writing ionic equations for redox reactions.
Use the BACK button on your browser to return to this page.

Using potassium dichromate(VI) as an oxidising agent in organic chemistry


Potassium dichromate(VI) solution acidified with dilute sulphuric acid is commonly used as
an oxidising agent in organic chemistry. It is a reasonably strong oxidising agent without
being so powerful that it takes the whole of the organic molecule to pieces! (Potassium
manganate(VII) solution has some tendency to do that.)
It is used to:

oxidise secondary alcohols to ketones;

oxidise primary alcohols to aldehydes;

oxidise primary alcohols to carboxylic acids.

For example, with ethanol (a primary alcohol), you can get either ethanal (an aldehyde) or
ethanoic acid (a carboxylic acid) depending on the conditions.

If the alcohol is in excess, and you distil off the aldehyde as soon as it is formed, you
get ethanal as the main product.

If the oxidising agent is in excess, and you don't allow the product to escape - for
example, by heating the mixture under reflux (heating the flask with a condenser
placed vertically in the neck) - you get ethanoic acid.

In organic chemistry, these equations are often simplified to concentrate on what is


happening to the organic molecules. For example, the last two could be written:

The oxygen written in square brackets just means "oxygen from an oxidising agent".
Note: These are not a proper substitute for real equations. Only use them if your examiners are happy
with them. Check your syllabus and look at past papers and mark schemes.
If you are working towards a UK-based exam and don't have these things, you can find out how to get
hold of them by going to thesyllabuses page.

Using this same reaction to make chrome alum crystals


You will find chrome alum under all sorts of different names:

chrome alum

potassium chromium(III) sulphate

chromium(III) potassium sulphate

chromium(III) potassium sulphate-12-water

chromium(III) potassium sulphate dodecahydrate

. . . and various others!


You will also find variations on its formula. For example:

CrK(SO4)2,12H2O

Cr2(SO4)3,K2SO4,24H2O

K2SO4,Cr2(SO4)3,24H2O

The first of these formulae is just the other ones divided by two and rearranged a bit.
Personally, I prefer the second one because it is easier to understand what is going on.
Chrome alum is known as a double salt. If you mix solutions of potassium sulphate and
chromium(III) sulphate so that their molar concentrations are the same, the solution
behaves just like you would expect of such a mixture. It gives the reactions of chromium(III)
ions, of potassium ions, and of sulphate ions.
However, if you crystallise it, instead of getting mixed crystals of potassium sulphate and
chromium(III) sulphate, the solution crystallises as single deep purple crystals. These are
"chrome alum".
Chrome alum crystals can be made by reducing acidified potassium dichromate(VI)
solution using ethanol, and then crystallising the resulting solution.
Assuming you use an excess of ethanol, the main organic product will be ethanal - and
we've already seen this equation above:

This ionic equation obviously doesn't contain the spectator ions, potassium and sulphate.

Feeding those back in gives the full equation:

If you look at the top line on the right-hand side of the equation, you will see that the
chromium(III) sulphate and potassium sulphate are produced in exactly the right
proportions to make the double salt.
What you do, then, is this:
Note: I am not giving quantities and exact conditions - there are practical and safety considerations
which make me reluctant to do that. If you want precise details, they aren't difficult to find.

You start with a solution of potassium dichromate(VI) to which has been added some
concentrated sulphuric acid. The solution is then cooled by standing it in ice.
An excess of ethanol is added slowly with stirring so that the temperature doesn't rise too
much.
Note: If the solution gets too warm, you get a ligand exchange reaction between water molecules
attached to the chromium(III) ions produced and sulphate ions in the solution. This leads to the green
form of chromium(III) sulphate described higher up the page. To make chrome alum crystals, you have to
stop this happening.

When all the ethanol has been added, the solution is left over-night, preferably in a
refrigerator, to crystallise. The crystals can be separated from the remaining solution,
washed with a little pure water and then dried with filter paper.

Using potassium dichromate(VI) as an oxidising agent in titrations


Potassium dichromate(VI) is often used to estimate the concentration of iron(II) ions in
solution. It serves as an alternative to using potassium manganate(VII) solution.

Note: Potassium manganate(VII) titrations are described fully on the page about manganese chemistry.

In practice
There are advantages and disadvantages in using potassium dichromate(VI).
Advantages

Potassium dichromate(VI) can be used as a primary standard. That means that it


can be made up to give a stable solution of accurately known concentration. That
isn't true of potassium manganate(VII).

Potassium dichromate(VI) can be used in the presence of chloride ions (as long as
the chloride ions aren't present in very high concentration).
Potassium manganate(VII) oxidises chloride ions to chlorine; potassium
dichromate(VI) isn't quite a strong enough oxidising agent to do this. That means
that you don't get unwanted side reactions with the potassium dichromate(VI)
soution.

Disadvantage

The main disadvantage lies in the colour change. Potassium manganate(VII)


titrations are self-indicating. As you run the potassium manganate(VII) solution into
the reaction, the solution becomes colourless. As soon as you add as much as one
drop too much, the solution becomes pink - and you know you have reached the
end point.
Unfortunately potassium dichromate(VI) solution turns green as you run it into the
reaction, and there is no way you could possibly detect the colour change when you
have one drop of excess orange solution in a strongly coloured green solution.
With potassium dichromate(VI) solution you have to use a separate indicator, known
as a redox indicator. These change colour in the presence of an oxidising agent.
There are several such indicators - such as diphenylamine sulphonate. This gives a
violet-blue colour in the presence of excess potassium dichromate(VI) solution.

However, the colour is made difficult by the strong green also present. The end point
of a potassium dichromate(VI) titration isn't as easy to see as the end point of a
potassium manganate(VII) one.
The calculation
The half-equation for the dichromate(VI) ion is:

. . . and for the iron(II) ions is:

Combining these gives:

You can see that the reacting proportions are 1 mole of dichromate(VI) ions to 6 moles of
iron(II) ions.
Once you have established that, the titration calculation is going to be just like any other
one.
Note: If you aren't very good at doing titration calculations, you might be interested in my chemistry
calculations book.

Testing for chromate(VI) ions in solution


Typically, you would be looking at solutions containing sodium, potassium or ammonium
chromate(VI). Most chromates are at best only slightly soluble; many we would count as
insoluble.
The bright yellow colour of a solution suggests that it would be worth testing for
chromate(VI) ions.
Testing by adding an acid

If you add some dilute sulphuric acid to a solution containing chromate(VI) ions, the colour
changes to the familiar orange of dichromate(VI) ions.

You can't rely on this as a test for chromate(VI) ions, however. It might be that you have a
solution containing an acid-base indicator which happens to have the same colour change!
Testing by adding barium chloride (or nitrate) solution
Chromate(VI) ions will give a yellow precipitate of barium chromate(VI).

Note: The precipitate colour is very similar to the background colour I use on Chemguide pages, which
makes the last diagram a bit difficult to see. The photo on the right is by courtesy of Professor Stanley G.
Smith of the The University of Illinois at Urbana-Champaign.

Testing by adding lead(II) nitrate solution


Chromate(VI) ions will give a bright yellow precipitate of lead(II) chromate(VI). This is the

original "chrome yellow" paint pigment.

IONISATION ENERGY

This page explains what first ionisation energy is, and then looks at the way it varies
around the Periodic Table - across periods and down groups. It assumes that you
know about simple atomic orbitals, and can write electronic structures for simple
atoms. You will find a link at the bottom of the page to a similar description of
successive ionisation energies (second, third and so on).
Important! If you aren't reasonable happy about atomic orbitals and electronic structures you
should follow these links before you go any further.

Defining first ionisation energy


Definition
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+.
This is more easily seen in symbol terms.

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


Worried about moles? Don't be! For now, just take it as a measure of a particular amount of a
substance. It isn't worth worrying about at the moment.

Things to notice about the equation


The state symbols - (g) - are essential. When you are talking about ionisation energies,
everything must be present in the gas state.
Ionisation energies are measured in kJ mol-1 (kilojoules per mole). They vary in size from
381 (which you would consider very low) up to 2370 (which is very high).
All elements have a first ionisation energy - even atoms which don't form positive ions in
test tubes. The reason that helium (1st I.E. = 2370 kJ mol -1) doesn't normally form a
positive ion is because of the huge amount of energy that would be needed to remove one
of its electrons.

Patterns of first ionisation energies in the Periodic Table


The first 20 elements

First ionisation energy shows periodicity. That means that it varies in a repetitive way as
you move through the Periodic Table. For example, look at the pattern from Li to Ne, and

then compare it with the identical pattern from Na to Ar.


These variations in first ionisation energy can all be explained in terms of the structures of
the atoms involved.

Factors affecting the size of ionisation energy


Ionisation energy is a measure of the energy needed to pull a particular electron away from
the attraction of the nucleus. A high value of ionisation energy shows a high attraction
between the electron and the nucleus.
The size of that attraction will be governed by:
The charge on the nucleus.
The more protons there are in the nucleus, the more positively charged the nucleus is, and
the more strongly electrons are attracted to it.
The distance of the electron from the nucleus.
Attraction falls off very rapidly with distance. An electron close to the nucleus will be much
more strongly attracted than one further away.
The number of electrons between the outer electrons and the nucleus.
Consider a sodium atom, with the electronic structure 2,8,1. (There's no reason why you
can't use this notation if it's useful!)
If the outer electron looks in towards the nucleus, it doesn't see the nucleus sharply.
Between it and the nucleus there are the two layers of electrons in the first and second
levels. The 11 protons in the sodium's nucleus have their effect cut down by the 10 inner
electrons. The outer electron therefore only feels a net pull of approximately 1+ from the
centre. This lessening of the pull of the nucleus by inner electrons is known
as screeningor shielding.
Warning! Electrons don't, of course, "look in" towards the nucleus - and they don't "see" anything
either! But there's no reason why you can't imagine it in these terms if it helps you to visualise

what's happening. Just don't use these terms in an exam! You may get an examiner who is upset
by this sort of loose language.

Whether the electron is on its own in an orbital or paired with another electron.
Two electrons in the same orbital experience a bit of repulsion from each other. This offsets
the attraction of the nucleus, so that paired electrons are removed rather more easily than
you might expect.

Explaining the pattern in the first few elements


Hydrogen has an electronic structure of 1s1. It is a very small atom, and the single electron
is close to the nucleus and therefore strongly attracted. There are no electrons screening it
from the nucleus and so the ionisation energy is high (1310 kJ mol -1).
Helium has a structure 1s2. The electron is being removed from the same orbital as in
hydrogen's case. It is close to the nucleus and unscreened. The value of the ionisation
energy (2370 kJ mol-1) is much higher than hydrogen, because the nucleus now has 2
protons attracting the electrons instead of 1.
Lithium is 1s22s1. Its outer electron is in the second energy level, much more distant from
the nucleus. You might argue that that would be offset by the additional proton in the
nucleus, but the electron doesn't feel the full pull of the nucleus - it is screened by the
1s2 electrons.

You can think of the electron as feeling a net 1+ pull from the centre (3 protons offset by
the two 1s2 electrons).
If you compare lithium with hydrogen (instead of with helium), the hydrogen's electron also
feels a 1+ pull from the nucleus, but the distance is much greater with lithium. Lithium's first
ionisation energy drops to 519 kJ mol-1 whereas hydrogen's is 1310 kJ mol-1.

The patterns in periods 2 and 3


Talking through the next 17 atoms one at a time would take ages. We can do it much more
neatly by explaining the main trends in these periods, and then accounting for the
exceptions to these trends.
The first thing to realise is that the patterns in the two periods are identical - the difference
being that the ionisation energies in period 3 are all lower than those in period 2.

Explaining the general trend across periods 2 and 3


The general trend is for ionisation energies to increase across a period.
In the whole of period 2, the outer electrons are in 2-level orbitals - 2s or 2p. These are all
the same sort of distances from the nucleus, and are screened by the same 1s 2 electrons.
The major difference is the increasing number of protons in the nucleus as you go from
lithium to neon. That causes greater attraction between the nucleus and the electrons and
so increases the ionisation energies. In fact the increasing nuclear charge also drags the
outer electrons in closer to the nucleus. That increases ionisation energies still more as
you go across the period.
Note: Factors affecting atomic radius are covered on a separate page.

In period 3, the trend is exactly the same. This time, all the electrons being removed are in
the third level and are screened by the 1s22s22p6 electrons. They all have the same sort of
environment, but there is an increasing nuclear charge.
Why the drop between groups 2 and 3 (Be-B and Mg-Al)?
The explanation lies with the structures of boron and aluminium. The outer electron is
removed more easily from these atoms than the general trend in their period would
suggest.

Be

1s22s2

1st I.E. = 900 kJ mol-1

1s22s22px1

1st I.E. = 799 kJ mol-1

You might expect the boron value to be more than the beryllium value because of the extra
proton. Offsetting that is the fact that boron's outer electron is in a 2p orbital rather than a
2s. 2p orbitals have a slightly higher energy than the 2s orbital, and the electron is, on
average, to be found further from the nucleus. This has two effects.

The increased distance results in a reduced attraction and so a reduced ionisation


energy.

The 2p orbital is screened not only by the 1s2 electrons but, to some extent, by the
2s2 electrons as well. That also reduces the pull from the nucleus and so lowers the
ionisation energy.

The explanation for the drop between magnesium and aluminium is the same, except that
everything is happening at the 3-level rather than the 2-level.
Mg

1s22s22p63s2

1st I.E. = 736 kJ mol-1

Al

1s22s22p63s23px1

1st I.E. = 577 kJ mol-1

The 3p electron in aluminium is slightly more distant from the nucleus than the 3s, and
partially screened by the 3s2 electrons as well as the inner electrons. Both of these factors
offset the effect of the extra proton.
Warning! You might possibly come across a text book which describes the drop between group 2
and group 3 by saying that a full s2 orbital is in some way especially stable and that makes the
electron more difficult to remove. In other words, that the fluctuation is because the group 2 value
for ionisation energy is abnormally high. This is quite simply wrong! The reason for the fluctuation is
because the group 3 value is lower than you might expect for the reasons we've looked at.

Why the drop between groups 5 and 6 (N-O and P-S)?


Once again, you might expect the ionisation energy of the group 6 element to be higher
than that of group 5 because of the extra proton. What is offsetting it this time?
N

1s22s22px12py12pz1

1st I.E. = 1400 kJ mol-1

1s22s22px22py12pz1

1st I.E. = 1310 kJ mol-1

The screening is identical (from the 1s2 and, to some extent, from the 2s2 electrons), and
the electron is being removed from an identical orbital.
The difference is that in the oxygen case the electron being removed is one of the 2p x2 pair.
The repulsion between the two electrons in the same orbital means that the electron is
easier to remove than it would otherwise be.
The drop in ionisation energy at sulphur is accounted for in the same way.

Trends in ionisation energy down a group


As you go down a group in the Periodic Table ionisation energies generally fall. You have
already seen evidence of this in the fact that the ionisation energies in period 3 are all less
than those in period 2.
Taking Group 1 as a typical example:

Why is the sodium value less than that of lithium?


There are 11 protons in a sodium atom but only 3 in a lithium atom, so the nuclear charge
is much greater. You might have expected a much larger ionisation energy in sodium, but
offsetting the nuclear charge is a greater distance from the nucleus and more screening.
Li

1s22s1

1st I.E. = 519 kJ mol-1

Na

1s22s22p63s1

1st I.E. = 494 kJ mol-1

Lithium's outer electron is in the second level, and only has the 1s 2 electrons to screen it.
The 2s1 electron feels the pull of 3 protons screened by 2 electrons - a net pull from the

centre of 1+.
The sodium's outer electron is in the third level, and is screened from the 11 protons in the
nucleus by a total of 10 inner electrons. The 3s 1 electron also feels a net pull of 1+ from the
centre of the atom. In other words, the effect of the extra protons is compensated for by the
effect of the extra screening electrons. The only factor left is the extra distance between the
outer electron and the nucleus in sodium's case. That lowers the ionisation energy.
Similar explanations hold as you go down the rest of this group - or, indeed, any other
group.

Trends in ionisation energy in a transition series

Apart from zinc at the end, the other ionisation energies are all much the same.
All of these elements have an electronic structure [Ar]3d n4s2 (or 4s1 in the cases of
chromium and copper). The electron being lost always comes from the 4s orbital.
Note: The 4s orbital has a higher energy than the 3d in the transition elements. That means that it
is a 4s electron which is lost from the atom when it forms an ion. It also means that the 3d orbitals
are slightly closer to the nucleus than the 4s - and so offer some screening.
Confusingly, this is inconsistent with what we say when we use the Aufbau Principle to work out the
electronic structures of atoms.
I have discussed this in detail in the page about the order of filling 3d and 4s orbitals.
If you are a teacher or a very confident student then you might like to follow this link.
If you aren't so confident, or are coming at this for the first time, I suggest that you ignore it.
Remember that the Aufbau Principle (which uses the assumption that the 3d orbitals fill after the
4s) is just a useful way of working out the structures of atoms, but that in real transition metal atoms

the 4s is actually the outer, higher energy orbital.

As you go from one atom to the next in the series, the number of protons in the nucleus
increases, but so also does the number of 3d electrons. The 3d electrons have some
screening effect, and the extra proton and the extra 3d electron more or less cancel each
other out as far as attraction from the centre of the atom is concerned.
The rise at zinc is easy to explain.
Cu

[Ar]3d104s1

1st I.E. = 745 kJ mol-1

Zn

[Ar]3d104s2

1st I.E. = 908 kJ mol-1

In each case, the electron is coming from the same orbital, with identical screening, but the
zinc has one extra proton in the nucleus and so the attraction is greater. There will be a
degree of repulsion between the paired up electrons in the 4s orbital, but in this case it
obviously isn't enough to outweigh the effect of the extra proton.
Note: This is actually very similar to the increase from, say, sodium to magnesium in the third
period. In that case, the outer electronic structure is going from 3s 1 to 3s2. Despite the pairing-up of
the electrons, the ionisation energy increases because of the extra proton in the nucleus. The
repulsion between the 3s electrons obviously isn't enough to outweigh this either.
I don't know why the repulsion between the paired electrons matters less for electrons in s orbitals
than in p orbitals (I don't even know whether you can make that generalisation!). I suspect that it
has to do with orbital shape and possibly the greater penetration of s electrons towards the nucleus,
but I haven't been able to find any reference to this anywhere. In fact, I haven't been able to find
anyone who even mentions repulsion in the context of paired s electrons!
If you have any hard information on this, could you contact me via the address on the about this
site page.

Ionisation energies and reactivity

The lower the ionisation energy, the more easily this change happens:

You can explain the increase in reactivity of the Group 1 metals (Li, Na, K, Rb, Cs) as you
go down the group in terms of the fall in ionisation energy. Whatever these metals react
with, they have to form positive ions in the process, and so the lower the ionisation energy,
the more easily those ions will form.
The danger with this approach is that the formation of the positive ion is only one stage in a
multi-step process.
For example, you wouldn't be starting with gaseous atoms; nor would you end up with
gaseous positive ions - you would end up with ions in a solid or in solution. The energy
changes in these processes also vary from element to element. Ideally you need to
consider the whole picture and not just one small part of it.
However, the ionisation energies of the elements are going to be major contributing factors
towards the activation energy of the reactions. Remember that activation energy is the
minimum energy needed before a reaction will take place. The lower the activation energy,
the faster the reaction will be - irrespective of what the overall energy changes in the
reaction are.
The fall in ionisation energy as you go down a group will lead to lower activation energies
and therefore faster reactions.
Note: You will find a page discussing this in more detail in the inorganic section of this site dealing
with the reactions of Group 2 metals with water.

THE ATOMIC HYDROGEN EMISSION SPECTRUM


This page introduces the atomic hydrogen emission spectrum, showing how it arises from
electron movements between energy levels within the atom. It also looks at how the

spectrum can be used to find the ionisation energy of hydrogen.

What is an emission spectrum?


Observing hydrogen's emission spectrum
A hydrogen discharge tube is a slim tube containing hydrogen gas at low pressure with an
electrode at each end. If you put a high voltage across this (say, 5000 volts), the tube lights
up with a bright pink glow.
If the light is passed through a prism or diffraction grating, it is split into its various colours.
What you would see is a small part of the hydrogen emission spectrum. Most of the
spectrum is invisible to the eye because it is either in the infra-red or the ultra-violet.
The photograph shows part of a hydrogen discharge tube on the left, and the three most
easily seen lines in the visible part of the spectrum on the right. (Ignore the "smearing" particularly to the left of the red line. This is caused by flaws in the way the photograph was
taken. See note below.)

Note: This photograph is by courtesy of Dr Rod Nave of the Department of Physics and Astronomy at
Georgia State University, Atlanta. The photograph comes from notes about the hydrogen spectrum in
his HyperPhysics pages on the University site. If you are interested in more than an introductory look at
the subject, that is a good place to go.
Ideally the photo would show three clean spectral lines - dark blue, cyan and red. The red smearing

which appears to the left of the red line, and other similar smearing (much more difficult to see) to the
left of the other two lines probably comes, according to Dr Nave, from stray reflections in the set-up, or
possibly from flaws in the diffraction grating. I have chosen to use this photograph anyway because a) I
think it is a stunning image, and b) it is the only one I have ever come across which includes a
hydrogen discharge tube and its spectrum in the same image.

Extending hydrogen's emission spectrum into the UV and IR


There is a lot more to the hydrogen spectrum than the three lines you can see with the
naked eye. It is possible to detect patterns of lines in both the ultra-violet and infra-red
regions of the spectrum as well.
These fall into a number of "series" of lines named after the person who discovered them.
The diagram below shows three of these series, but there are others in the infra-red to the
left of the Paschen series shown in the diagram.
The diagram is quite complicated, so we will look at it a bit at a time. Look first at the
Lyman series on the right of the diagram - this is the most spread out one and easiest to
see what is happening.

Note: The frequency scale is marked in PHz - that's petaHertz. You are familiar with prefixes like kilo

(meaning a thousand or 103 times), and mega (meaning a million or 106times). Peta means 1015 times.
So a value like 3 PHz means 3 x 1015 Hz. If you are worried about "Hertz", it just means "cycles per
second".

The Lyman series is a series of lines in the ultra-violet. Notice that the lines get closer and
closer together as the frequency increases. Eventually, they get so close together that it
becomes impossible to see them as anything other than a continuous spectrum. That's
what the shaded bit on the right-hand end of the series suggests.
Then at one particular point, known as the series limit, the series stops.
If you now look at the Balmer series or the Paschen series, you will see that the pattern is
just the same, but the series have become more compact. In the Balmer series, notice the
position of the three visible lines from the photograph further up the page.

Complicating everything - frequency and wavelength


You will often find the hydrogen spectrum drawn using wavelengths of light rather than
frequencies. Unfortunately, because of the mathematical relationship between the
frequency of light and its wavelength, you get two completely different views of the
spectrum if you plot it against frequency or against wavelength.
The relationship between frequency and wavelength
The mathematical relationship is:

Rearranging this gives equations for either wavelength or frequency.

What this means is that there is an inverse relationship between the two - a high frequency
means a low wavelength and vice versa.
Note: You will sometimes find frequency given the much more obvious symbol, f.

Drawing the hydrogen spectrum in terms of wavelength


This is what the spectrum looks like if you plot it in terms of wavelength instead of
frequency:

. . . and just to remind you what the spectrum in terms of frequency looks like:

Is this confusing? Well, I find it extremely confusing! So what do you do about it?
For the rest of this page I shall only look at the spectrum plotted against frequency,
because it is much easier to relate it to what is happening in the atom. Be aware that the
spectrum looks different depending on how it is plotted, but, other than that, ignore the
wavelength version unless it is obvious that your examiners want it. If you try to learn both
versions, you are only going to get them muddled up!
Note: Syllabuses probably won't be very helpful about this. You need to look at past papers and mark
schemes.
If you are working towards a UK-based exam and don't have these things, you can find out how to get
hold of them by going to the syllabuses page.

Explaining hydrogen's emission spectrum


The Balmer and Rydberg Equations
By an amazing bit of mathematical insight, in 1885 Balmer came up with a simple formula
for predicting the wavelength of any of the lines in what we now know as the Balmer series.
Three years later, Rydberg generalised this so that it was possible to work out the
wavelengths of any of the lines in the hydrogen emission spectrum.
What Rydberg came up with was:

RH is a constant known as the Rydberg constant.


n1 and n2 are integers (whole numbers). n2 has to be greater than n1. In other words, if n1 is,
say, 2 then n2 can be any whole number between 3 and infinity.
The various combinations of numbers that you can slot into this formula let you calculate
the wavelength of any of the lines in the hydrogen emission spectrum - and there is close
agreement between the wavelengths that you get using this formula and those found by
analysing a real spectrum.
Note: If you come across a version of Balmer's original equation, it won't look like this. In Balmer's
equation, n1 is always 2 - because that gives the wavelengths of the lines in the visible part of the
spectrum which is what he was interested in. His original equation was also organised differently. The
modern version shows more clearly what is going on.

You can also use a modified version of the Rydberg equation to calculate the frequency of
each of the lines. You can work out this version from the previous equation and the formula
relating wavelength and frequency further up the page.

Note: You may come across versions of the Rydberg equation where the n 1 and n2 are the other way
around, or they may even be swapped for letters like m and n. Whichever version you use, the bigger
number must always be the one at the bottom of the right-hand term - the one you take away. If you get
them the wrong way around, it is immediately obvious if you start to do a calculation, because you will
end up with a negative answer!

The origin of the hydrogen emission spectrum


The lines in the hydrogen emission spectrum form regular patterns and can be represented
by a (relatively) simple equation. Each line can be calculated from a combination of simple
whole numbers.
Why does hydrogen emit light when it is excited by being exposed to a high voltage and
what is the significance of those whole numbers?
When nothing is exciting it, hydrogen's electron is in the first energy level - the level closest
to the nucleus. But if you supply energy to the atom, the electron gets excited into a higher
energy level - or even removed from the atom altogether.
The high voltage in a discharge tube provides that energy. Hydrogen molecules are first
broken up into hydrogen atoms (hence the atomic hydrogen emission spectrum) and
electrons are then promoted into higher energy levels.
Suppose a particular electron was excited into the third energy level. This would tend to
lose energy again by falling back down to a lower level. It could do this in two different
ways.
It could fall all the way back down to the first level again, or it could fall back to the second
level - and then, in a second jump, down to the first level.

Tying particular electron jumps to individual lines in the spectrum


If an electron falls from the 3-level to the 2-level, it has to lose an amount of energy exactly
the same as the energy gap between those two levels. That energy which the electron
loses comes out as light (where "light" includes UV and IR as well as visible).
Each frequency of light is associated with a particular energy by the equation:

The higher the frequency, the higher the energy of the light.
If an electron falls from the 3-level to the 2-level, red light is seen. This is the origin of the

red line in the hydrogen spectrum. By measuring the frequency of the red light, you can
work out its energy. That energy must be exactly the same as the energy gap between the
3-level and the 2-level in the hydrogen atom.
The last equation can therefore be re-written as a measure of the energy gap between two
electron levels.

The greatest possible fall in energy will therefore produce the highest frequency line in the
spectrum. The greatest fall will be from the infinity level to the 1-level. (The significance of
the infinity level will be made clear later.)
The next few diagrams are in two parts - with the energy levels at the top and the spectrum
at the bottom.

If an electron fell from the 6-level, the fall is a little bit less, and so the frequency will be a
little bit lower. (Because of the scale of the diagram, it is impossible to draw in all the jumps
involving all the levels between 7 and infinity!)

. . . and as you work your way through the other possible jumps to the 1-level, you have
accounted for the whole of the Lyman series. The spacings between the lines in the
spectrum reflect the way the spacings between the energy levels change.

If you do the same thing for jumps down to the 2-level, you end up with the lines in the
Balmer series. These energy gaps are all much smaller than in the Lyman series, and so
the frequencies produced are also much lower.

The Paschen series would be produced by jumps down to the 3-level, but the diagram is
going to get very messy if I include those as well - not to mention all the other series with
jumps down to the 4-level, the 5-level and so on.

The significance of the numbers in the Rydberg equation


n1 and n2 in the Rydberg equation are simply the energy levels at either end of the jump
producing a particular line in the spectrum.
For example, in the Lyman series, n1 is always 1. Electrons are falling to the 1-level to
produce lines in the Lyman series. For the Balmer series, n 1 is always 2, because electrons
are falling to the 2-level.

n2 is the level being jumped from. We have already mentioned that the red line is produced
by electrons falling from the 3-level to the 2-level. In this case, then, n 2 is equal to 3.

The significance of the infinity level


The infinity level represents the highest possible energy an electron can have as a part of a
hydrogen atom. So what happens if the electron exceeds that energy by even the tiniest
bit?
The electron is no longer a part of the atom. The infinity level represents the point at which
ionisation of the atom occurs to form a positively charged ion.

Using the spectrum to find hydrogen's ionisation energy


When there is no additional energy supplied to it, hydrogen's electron is found at the 1level. This is known as its ground state. If you supply enough energy to move the electron
up to the infinity level, you have ionised the hydrogen.
The ionisation energy per electron is therefore a measure of the distance between the 1level and the infinity level. If you look back at the last few diagrams, you will find that that
particular energy jump produces the series limit of the Lyman series.
Note: Up to now we have been talking about the energy released when an electron falls from a higher
to a lower level. Obviously if a certain amount of energy is released when an electron falls from the
infinity level to the 1-level, that same amount will be needed to push the electron from the 1-level up to
the infinity level.

If you can determine the frequency of the Lyman series limit, you can use it to calculate the
energy needed to move the electron in one atom from the 1-level to the point of ionisation.
From that, you can calculate the ionisation energy per mole of atoms.
The problem is that the frequency of a series limit is quite difficult to find accurately from a
spectrum because the lines are so close together in that region that the spectrum looks

continuous.

Finding the frequency of the series limit graphically


Here is a list of the frequencies of the seven most widely spaced lines in the Lyman series,
together with the increase in frequency as you go from one to the next.

As the lines get closer together, obviously the increase in frequency gets less. At the series
limit, the gap between the lines would be literally zero.
That means that if you were to plot the increases in frequency against the actual frequency,
you could extrapolate (continue) the curve to the point at which the increase becomes
zero. That would be the frequency of the series limit.
In fact you can actually plot two graphs from the data in the table above. The
frequency difference is related to two frequencies. For example, the figure of 0.457 is found
by taking 2.467 away from 2.924. So which of these two values should you plot the 0.457
against?
It doesn't matter, as long as you are always consistent - in other words, as long as
you always plot the difference against either the higher or the lower figure. At the point you

are interested in (where the difference becomes zero), the two frequency numbers are the
same.
As you will see from the graph below, by plotting both of the possible curves on the same
graph, it makes it easier to decide exactly how to extrapolate the curves. Because these
are curves, they are much more difficult to extrapolate than if they were straight lines.

Both lines point to a series limit at about 3.28 x 10 15 Hz.


Note: Remember that 3.28 PHz is the same as 3.28 x 1015Hz. You can use the Rydberg equation to
calculate the series limit of the Lyman series as a check on this figure: n 1 = 1 for the Lyman series, and
n2 = infinity for the series limit. 1/(infinity)2 = zero. That gives a value for the frequency of 3.29 x 1015 Hz
- in other words the two values agree to within 0.3%.

So . . . now we can calculate the energy needed to remove a single electron from a

hydrogen atom. Remember the equation from higher up the page:

We can work out the energy gap between the ground state and the point at which the
electron leaves the atom by substituting the value we've got for frequency and looking up
the value of Planck's constant from a data book.

That gives you the ionisation energy for a single atom. To find the normally quoted
ionisation energy, we need to multiply this by the number of atoms in a mole of hydrogen
atoms (the Avogadro constant) and then divide by 1000 to convert it into kilojoules.

Note: It would be wrong to quote this to more than 3 significant figures. The value for the frequency
obtained from the graph is only to that accuracy.

This compares well with the normally quoted value for hydrogen's ionisation energy of

1312 kJ mol-1.
ELECTRON AFFINITY

This page explains what electron affinity is, and then looks at the factors that affect its size.
It assumes that you know about simple atomic orbitals, and can write electronic structures
for simple atoms.
Important! If you aren't reasonable happy about atomic orbitals and electronic
structures you should follow these links before you go any further.

First electron affinity


Ionisation energies are always concerned with the formation of positive ions. Electron
affinities are the negative ion equivalent, and their use is almost always confined to
elements in groups 6 and 7 of the Periodic Table.
Defining first electron affinity
The first electron affinity is the energy released when 1 mole of gaseous atoms each
acquire an electron to form 1 mole of gaseous 1- ions.
This is more easily seen in symbol terms.

It is the energy released (per mole of X) when this change happens.


First electron affinities have negative values. For example, the first electron affinity of
chlorine is -349 kJ mol-1. By convention, the negative sign shows a release of energy.

The first electron affinities of the group 7 elements


F

-328 kJ mol-1

Cl

-349 kJ mol-1

Br

-324 kJ mol-1

-295 kJ mol-1
Note: These values are based on the most recent research. If you are using a different
data source, you may have slightly different numbers. That doesn't matter - the pattern
will still be the same.

Is there a pattern?
Yes - as you go down the group, first electron affinities become less (in the sense that less
energy is evolved when the negative ions are formed). Fluorine breaks that pattern, and
will have to be accounted for separately.
The electron affinity is a measure of the attraction between the incoming electron and the
nucleus - the stronger the attraction, the more energy is released.
The factors which affect this attraction are exactly the same as those relating to ionisation
energies - nuclear charge, distance and screening.
Note: If you haven't read about ionisation energy recently, it might be a good idea to
follow this link before you go on. These factors are discussed in more detail on that
page than they are on this one.

The increased nuclear charge as you go down the group is offset by extra screening
electrons. Each outer electron in effect feels a pull of 7+ from the centre of the atom,
irrespective of which element you are talking about.
For example, a fluorine atom has an electronic structure of 1s 22s22px22py22pz1. It has 9
protons in the nucleus.
The incoming electron enters the 2-level, and is screened from the nucleus by the two

1s2 electrons. It therefore feels a net attraction from the nucleus of 7+ (9 protons less the 2
screening electrons).
By contrast, chlorine has the electronic structure 1s22s22p63s23px23py23pz1. It has 17
protons in the nucleus.
But again the incoming electron feels a net attraction from the nucleus of 7+ (17 protons
less the 10 screening electrons in the first and second levels).
Note: If you want to be fussy, there is also a small amount of screening by the 2s
electrons in fluorine and by the 3s electrons in chlorine. This will be approximately the
same in both these cases and so doesn't affect the argument in any way (apart from
complicating it!).

The over-riding factor is therefore the increased distance that the incoming electron finds
itself from the nucleus as you go down the group. The greater the distance, the less the
attraction and so the less energy is released as electron affinity.
Note: Comparing fluorine and chlorine isn't ideal, because fluorine breaks the trend in
the group. However, comparing chlorine and bromine, say, makes things seem more
difficult because of the more complicated electronic structures involved.
What we have said so far is perfectly true and applies to the fluorine-chlorine case as
much as to anything else in the group, but there's another factor which operates as well
which we haven't considered yet - and that over-rides the effect of distance in the case
of fluorine.

Why is fluorine out of line?


The incoming electron is going to be closer to the nucleus in fluorine than in any other of
these elements, so you would expect a high value of electron affinity.
However, because fluorine is such a small atom, you are putting the new electron into a
region of space already crowded with electrons and there is a significant amount of

repulsion. This repulsion lessens the attraction the incoming electron feels and so lessens
the electron affinity.
A similar reversal of the expected trend happens between oxygen and sulphur in Group 6.
The first electron affinity of oxygen (-142 kJ mol-1) is smaller than that of sulphur (-200 kJ
mol-1) for exactly the same reason that fluorine's is smaller than chlorine's.

Comparing Group 6 and Group 7 values


As you might have noticed, the first electron affinity of oxygen (-142 kJ mol -1) is less than
that of fluorine (-328 kJ mol-1). Similarly sulphur's (-200 kJ mol-1) is less than chlorine's (349 kJ mol-1). Why?
It's simply that the Group 6 element has 1 less proton in the nucleus than its next door
neighbour in Group 7. The amount of screening is the same in both.
That means that the net pull from the nucleus is less in Group 6 than in Group 7, and so
the electron affinities are less.

First electron affinity and reactivity


The reactivity of the elements in group 7 falls as you go down the group - fluorine is the
most reactive and iodine the least.
Often in their reactions these elements form their negative ions. At GCSE the impression is
sometimes given that the fall in reactivity is because the incoming electron is held less
strongly as you go down the group and so the negative ion is less likely to form. That
explanation looks reasonable until you include fluorine!
An overall reaction will be made up of lots of different steps all involving energy changes,
and you cannot safely try to explain a trend in terms of just one of those steps. Fluorine is
much more reactive than chlorine (despite the lower electron affinity) because the energy
released in other steps in its reactions more than makes up for the lower amount of energy
released as electron affinity.

Second electron affinity


You are only ever likely to meet this with respect to the group 6 elements oxygen and
sulphur which both form 2- ions.
Defining second electron affinity
The second electron affinity is the energy required to add an electron to each ion in 1 mole
of gaseous 1- ions to produce 1 mole of gaseous 2- ions.
This is more easily seen in symbol terms.

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


Why is energy needed to do this?
You are forcing an electron into an already negative ion. It's not going to go in willingly!
1st EA = -142 kJ mol-1
2nd EA = +844 kJ mol-1
The positive sign shows that you have to put in energy to perform this change. The second
electron affinity of oxygen is particularly high because the electron is being forced into a
small, very electron-dense space.

ATOMIC AND IONIC RADIUS

This page explains the various measures of atomic radius, and then looks at the way
it varies around the Periodic Table - across periods and down groups. It assumes
that you understand electronic structures for simple atoms written in s, p, d

notation.
Important! If you aren't reasonable happy about electronic structures you should follow this link
before you go any further.

ATOMIC RADIUS
Measures of atomic radius
Unlike a ball, an atom doesn't have a fixed radius. The radius of an atom can only be found
by measuring the distance between the nuclei of two touching atoms, and then halving that
distance.

As you can see from the diagrams, the same atom could be found to have a different
radius depending on what was around it.
The left hand diagram shows bonded atoms. The atoms are pulled closely together and so
the measured radius is less than if they are just touching. This is what you would get if you
had metal atoms in a metallic structure, or atoms covalently bonded to each other. The
type of atomic radius being measured here is called the metallic radius or the covalent
radiusdepending on the bonding.
The right hand diagram shows what happens if the atoms are just touching. The attractive
forces are much less, and the atoms are essentially "unsquashed". This measure of atomic
radius is called the van der Waals radius after the weak attractions present in this
situation.
Note: If you want to explore these various types of bonding this link will take you to the bonding
menu.

Trends in atomic radius in the Periodic Table


The exact pattern you get depends on which measure of atomic radius you use - but the
trends are still valid.
The following diagram uses metallic radii for metallic elements, covalent radii for elements
that form covalent bonds, and van der Waals radii for those (like the noble gases) which
don't form bonds.
Trends in atomic radius in Periods 2 and 3

Trends in atomic radius down a group


It is fairly obvious that the atoms get bigger as you go down groups. The reason is equally
obvious - you are adding extra layers of electrons.
Trends in atomic radius across periods
You have to ignore the noble gas at the end of each period. Because neon and argon don't
form bonds, you can only measure their van der Waals radius - a case where the atom is
pretty well "unsquashed". All the other atoms are being measured where their atomic
radius is being lessened by strong attractions. You aren't comparing like with like if you
include the noble gases.

Leaving the noble gases out, atoms get smaller as you go


across a period.

If you think about it, the metallic or covalent radius is going to be a measure of the distance
from the nucleus to the electrons which make up the bond. (Look back to the left-hand side

of the first diagram on this page if you aren't sure, and picture the bonding electrons as
being half way between the two nuclei.)
From lithium to fluorine, those electrons are all in the 2-level, being screened by the
1s2 electrons. The increasing number of protons in the nucleus as you go across the period
pulls the electrons in more tightly. 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 2s 2 electrons in the
cases of the elements from boron to fluorine where the bonding involves the p electrons.
In 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 2s
electrons as such.
If you don't know about hybridisation, just ignore this comment - you won't need it for UK A level
purposes anyway.

In the period from sodium to chlorine, the same thing happens. The size of the atom is
controlled by the 3-level bonding electrons being pulled closer to the nucleus by increasing
numbers of protons - in each case, screened by the 1- and 2-level electrons.

Trends in the transition elements

Although there is a slight contraction at the beginning of the series, the atoms are all much
the same size.
The size is determined by the 4s electrons. The pull of the increasing number of protons in
the nucleus is more or less offset by the extra screening due to the increasing number of
3d electrons.

Note: The 4s orbital has a higher energy than the 3d in the transition elements. That means that it is
a 4s electron which is lost from the atom when it forms an ion. It also means that the 3d orbitals are
slightly closer to the nucleus than the 4s - and so offer some screening.
Confusingly, this is inconsistent with what we say when we use the Aufbau Principle to work out the
electronic structures of atoms.
I have discussed this in detail in the page about the order of filling 3d and 4s orbitals.
If you are a teacher or a very confident student then you might like to follow this link.
If you aren't so confident, or are coming at this for the first time, I suggest that you ignore it.
Remember that the Aufbau Principle (which uses the assumption that the 3d orbitals fill after the 4s)
is just a useful way of working out the structures of atoms, but that in real transition metal atoms the
4s is actually the outer, higher energy orbital.

IONIC RADIUS
A warning!
Ionic radii are difficult to measure with any degree of certainty, and vary according to the
environment of the ion. For example, it matters what the co-ordination of the ion is (how
many oppositely charged ions are touching it), and what those ions are.
There are several different measures of ionic radii in use, and these all differ from each
other by varying amounts. It means that if you are going to make reliable comparisons
using ionic radii, they have to come from the same source.
What you have to remember is that there are quite big uncertainties in the use of ionic
radii, and that trying to explain things in fine detail is made difficult by those uncertainties.
What follows will be adequate for UK A level (and its various equivalents), but detailed
explanations are too complicated for this level.

Trends in ionic radius in the Periodic Table

Trends in ionic radius down a group


This is the easy bit! As you add extra layers of electrons as you go down a group, the ions
are bound to get bigger. The two tables below show this effect in Groups 1 and 7.
electronic structure
of ion

ionic radius (nm)

Li+

0.076

Na+

2, 8

0.102

K+

2, 8, 8

0.138

Rb+

2, 8, 18, 8

0.152

Cs+

2, 8, 18, 18, 8

0.167

electronic structure
of ion

ionic radius (nm)

F-

2, 8

0.133

Cl-

2, 8, 8

0.181

Br-

2, 8, 18, 8

0.196

I-

2, 8, 18, 18, 8

0.220

Note: These figures all come from the Database of Ionic Radii from Imperial College London. I have
converted them from Angstroms to nm (nanometres), which are more often used in the data tables
that you are likely to come across.
If you are interested, 1 Angstrom is 10-10 m; 1 nm = 10-9 m. To convert from Angstroms to nm, you
have to divide by 10, so that 1.02 Angstroms becomes 0.102 nm. You may also come across tables

listing values in pm (picometres) which are 10-12 m. A value in pm will look like, for example, for
chlorine, 181 pm rather than 0.181 nm. Don't worry if you find this confusing. Just use the values you
are given in whatever units you are given.
For comparison purposes, all the values relate to 6-co-ordinated ions (the same arrangement as in
NaCl, for example). CsCl actually crystallises in an 8:8-co-ordinated structure - so you couldn't
accurately use these values for CsCl. The 8-co-ordinated ionic radius for Cs is 0.174 nm rather than
0.167 for the 6-co-ordinated version.

Trends in ionic radius across a period


Let's look at the radii of the simple ions formed by elements as you go across Period 3 of
the Periodic Table - the elements from Na to Cl.

no of protons

Na+

Mg2+

Al3+

P3-

S2-

Cl-

11

12

13

15

16

17

electronic
structure of ion

2,8

2,8

2,8

2,8,8

2,8,8

2,8,8

ionic radius (nm)

0.102

0.072

0.054

(0.212)

0.184

0.181

Note: The table misses out silicon which doesn't form a simple ion. The phosphide ion radius is in
brackets because it comes from a different data source, and I am not sure whether it is safe to
compare it. The values for the oxide and chloride ions agree in the different source, so it is probably
OK. The values are again for 6-co-ordination, although I can't guarantee that for the phosphide
figure.

First of all, notice the big jump in ionic radius as soon as you get into the negative ions. Is
this surprising? Not at all - you have just added a whole extra layer of electrons.
Notice that, within the series of positive ions, and the series of negative ions, that the ionic

radii fall as you go across the period. We need to look at the positive and negative ions
separately.
The positive ions
In each case, the ions have exactly the same electronic structure - they are said to
be isoelectronic. However, the number of protons in the nucleus of the ions is increasing.
That will tend to pull the electrons more and more towards the centre of the ion - causing
the ionic radii to fall. That is pretty obvious!
The negative ions
Exactly the same thing is happening here, except that you have an extra layer of electrons.
What needs commenting on, though is how similar in size the sulphide ion and the chloride
ion are. The additional proton here is making hardly any difference.
The difference between the size of similar pairs of ions actually gets even smaller as you
go down Groups 6 and 7. For example, the Te 2- ion is only 0.001 nm bigger than the I- ion.
As far as I am aware there is no simple explanation for this - certainly not one which can be
used at this level. This is a good illustration of what I said earlier - explaining things
involving ionic radii in detail is sometimes very difficult.

Trends in ionic radius for some more isoelectronic ions


This is only really a variation on what we have just been talking about, but fits negative and
positive isoelectronic ions into the same series of results. Remember that isoelectronic ions
all have exactly the same electron arrangement.
N3-

O2-

F-

Na+

Mg2+

Al3+

11

12

13

no of protons
electronic
structure of ion

2, 8

2, 8

2, 8

2, 8

2, 8

2, 8

ionic radius (nm)

(0.171)

0.140

0.133

0.102

0.072

0.054

Note: The nitride ion value is in brackets because it came from a different source, and I don't know
for certain whether it relates to the same 6-co-ordination as the rest of the ions. This matters. My
main source only gave a 4-co-ordinated value for the nitride ion, and that was 0.146 nm.
You might also be curious as to how the neutral neon atom fits into this sequence. Its van der Waals
radius is 0.154 or 0.160 nm (depending on which source you look the value up in) - bigger than the
fluoride ion. You can't really sensibly compare a van der Waals radius with the radius of a bonded
atom or ion.

You can see that as the number of protons in the nucleus of the ion increases, the
electrons get pulled in more closely to the nucleus. The radii of the isoelectronic ions
therefore fall across this series.

Questions to test your understanding


If this is the first set of questions you have done, please read the introductory pagebefore you start. You will
need to use the BACK BUTTON on your browser to come back here afterwards.
questions on atomic and ionic radius
answers
There are no questions to test the rest of this page.

The relative sizes of ions and atoms


You probably won't have noticed, but nowhere in what you have read so far has there been
any need to talk about the relative sizes of the ions and the atoms they have come from.
Neither (as far as I can tell from the syllabuses) do any of the current UK-based exams for
16 - 18 year olds ask for this specifically in their syllabuses.
However, it is very common to find statements about the relative sizes of ions and atoms. I

am fairly convinced that these statements are faulty, and I would like to attack the problem
head-on rather than just ignoring it.
Important!
For 10 years, until I rewrote this ionic radius section in August 2010, I included what is in
the box below. You will find this same information and explanation in all sorts of books and
on any number of websites aimed at this level. At least one non-UK A level syllabus has a
statement which specifically asks for this.

Ions aren't the same size as the atoms they come from. Compare the sizes of sodium
and chloride ions with the sizes of sodium and chlorine atoms.

Positive ions
Positive ions are smaller than the atoms they come from. Sodium is 2,8,1; Na + is 2,8.
You've lost a whole layer of electrons, and the remaining 10 electrons are being pulled
in by the full force of 11 protons.
Negative ions
Negative ions are bigger than the atoms they come from. Chlorine is 2,8,7; Cl - is 2,8,8.
Although the electrons are still all in the 3-level, the extra repulsion produced by the
incoming electron causes the atom to expand. There are still only 17 protons, but they
are now having to hold 18 electrons.

However, I was challenged by an experienced teacher about the negative ion explanation,
and that forced me to think about it carefully for the first time. I am now convinced that the
facts and the explanation relating to negative ions are simply illogical.
As far as I can tell, no UK-based syllabus mentions the relative sizes of atoms and ions (as
of August 2010), but you should check past papers and mark schemes to see whether

questions have sneaked in.


The rest of this page discusses the problems that I can see, and is really aimed at
teachers and others, rather than at students.
If you are a student, look carefully at your syllabus, and past exam questions and mark
schemes, to find out whether you need to know about this. If you don't need to know about
it, stop reading now (unless, of course, you are interested in a bit of controversy!).
If you do need to know it, then you will have to learn what is in the box, even if, as I
believe, it is wrong. If you like your chemistry to be simple, ignore the rest of the page,
because you risk getting confused about what you need to know.
If you have expert knowledge of this topic, and can find any flaws in what I am saying,
then please contact me via the address on the about this site page.

Choosing the right atomic radius to compare with


This is at the heart of the problem.
The diagrams in the box above, and similar ones that you will find elsewhere, use the
metallic radius as the measure of atomic radius for metals, and the covalent radius for nonmetals. I want to focus on the non-metals, because that is where the main problem lies.
You are, of course, perfectly free to compare the radius of an ion with whatever measure of
atomic radius you choose. The problem comes in relating your choice of atomic radius to
the "explanation" of the differences.
It is perfectly true that negative ions have radii which are significantly bigger than the
covalent radius of the atom in question. And the argument then goes that the reason for
this is that if you add one or more extra electrons to the atom, inter-electron repulsions
cause the atom to expand. Therefore the negative ion is bigger than the atom.
This seems to me to be completely inconsistent. If you add one or more extra electrons to
the atom, you aren't adding them to a covalently bound atom. You can't simply add
electrons to a covalently-bound chlorine atom, for example - chlorine's existing electrons
have reorganised themselves into new molecular orbitals which bind the atoms together.
In a covalently-bound atom, there is simply no room to add extra electrons.

So if you want to use the electron repulsion explanation, the implication is that you are
adding the extra electrons to a raw atom with a simple uncombined electron arrangement.
In other words, if you were talking about, say, chlorine, you are adding an extra electron to
chlorine with a configuration of 2,8,7 - not to covalently bound chlorine atoms in which the
arrangement of the electrons has been altered by sharing.
That means that the comparison that you ought to be making isn't with the shortened
covalent radius, but with the much larger van der Waals radius - the only available measure
of the radius of an uncombined atom.
So what happens if you make that comparison?

Group 7
vdW radius (nm)

ionic radius of X- (nm)

0.147

0.133

Cl

0.175

0.181

Br

0.185

0.196

0.198

0.220

vdW radius (nm)

ionic radius of X2- (nm)

0.152

0.140

0.180

0.184

Group 6

Se

0.190

0.198

Te

0.206

0.221

Group 5
vdW radius (nm)

ionic radius of X3- (nm)

0.155

0.171

0.180

0.212

As we have already discussed above, measurements of ionic radii are full of uncertainties.
That is also true of van der Waals radii. The table uses one particular set of values for
comparison purposes. If you use data from different sources, you will find differences in the
patterns - including which of the species (ion or atom) is bigger.
These ionic radius values are for 6-co-ordinated ions (with a slight question mark over the
nitride and phosphide ion figures). But you may remember that I said that ionic radius
changes with co-ordination. Nitrogen is a particularly good example of this.
4-co-ordinated nitride ions have a radius of 0.146 nm. In other words if you look at one of
the co-ordinations, the nitride ion is bigger than the nitrogen atom; in the other case, it is
smaller. Making a general statement that nitride ions are bigger or smaller than nitrogen
atoms is impossible.

So what is it safe to say about the facts?


For most, but not all, negative ions, the radius of the ion is bigger than that of the atom, but
the difference is nothing like as great as is shown if you incorrectly compare ionic radii with
covalent radii. There are also important exceptions.
I can't see how you can make any real generalisations about this, given the uncertainties in

the data.

And what is it safe to say about the explanation?


If there are any additional electron-electron repulsions on adding extra electrons, they must
be fairly small. This is particularly shown if you consider some pairs of isoelectronic ions.
You would have thought that if repulsion was an important factor, then the radius of, say a
sulphide ion, with two negative charges would be significantly larger than a chloride ion
with only one. The difference should actually be even more marked, because the sulphide
electrons are being held by only 16 protons rather than the 17 in the chlorine case.
On this repulsion theory, the sulphide ion shouldn't just be a little bit bigger than a chloride
ion - it should be a lot bigger. The same effect is shown with selenide and bromide, and
with telluride and iodide ions. In the last case, there is virtually no difference in the sizes of
the 2- and 1- ions.
So if there is some repulsion playing a part in this, it certainly doesn't look as if it is playing
a major part.

What about positive ions?


Whether you choose to use van der Waals radii or metallic radii as a measure of the atomic
radius, for metals the ionic radius is smaller than either, so the problem doesn't exist to the
same extent. It is true that the ionic radius of a metal is less than its atomic radius (however
vague you are about defining this).
The explanation (at least as long as you only consider positive ions from Groups 1, 2 and
3) in terms of losing a complete layer of electrons is also acceptable.

Conclusion
It seems to me that, for negative ions, it is completely illogical to compare ionic radii with

covalent radii if you want to use the electron repulsion explanation.


If you compare the ionic radii of negative ions with the van der Waals radii of the atoms
they come from, the uncertainties in the data make it very difficult to make any reliable
generalisations.
The similarity in sizes of pairs of isoelectronic ions from Groups 6 and 7 calls into question
how important repulsion is in any explanation.
Having spent more than a week working on this, and discussing it with input from some
very knowledgable people, I don't think there is any explanation which is simple enough to
give to most students at this level. It would seem to me to be better that these ideas about
relative sizes of atoms and ions are just dropped.
At this level, you can describe and explain simple periodic trends in atomic radii in the way I
did further up this page, without even thinking about the relative sizes of the atoms and
ions. Personally, I would be more than happy never to think about this again for the rest of
my life!