Chemguide: Support for CIE A level Chemistry

Learning outcome 1(a)

Relative isotopic mass
Isotopes are atoms of the same element (and so with the same number of protons
and electrons), but with different masses due to having different numbers of
neutrons.
So, for example, chlorine has two different sorts of atoms each of which has 17
protons and 17 electrons. However, one of these atoms has 18 neutrons whereas
the other has 20.
All the chemical properties of the atoms are the same because they have the
same numbers of protons and electrons, but they have different masses.
The mass of an atom is incredibly small, and it doesn't make sense to use standard
units like grams to measure it. Instead masses are measured on a scale based on
the mass of an atom of the 12C isotope.
On the 12C scale, the 12C isotope is given a mass of exactly 12 units, and the
masses of all other isotopes are measured on the same scale.
For example, an atom of 24Mg is twice as heavy as an atom of 12C, and so is
given a relative isotopic mass of 24. An atom of the 1H isotope is only 1/12 of the
mass of the 12C isotope and so is given a relative isotopic mass of 1.

There are two equivalent ways in which you can define relative isotopic mass.
They mean exactly the same thing.
Either:

The relative isotopic mass of an isotope is the mass of the isotope on a scale
on which a carbon-12 atom has a mass of exactly 12 units.

Or:
The relative isotopic mass of an isotope is the mass of the isotope

relative to 1/12 of the mass of a carbon-12 atom.

Relative atomic mass, Ar

Similarly, relative atomic mass can be defined in two exactly equivalent ways:
Either:

The relative atomic mass of an element is the weighted average of the

masses of its isotopes on a scale on which a carbon-12 atom has a mass of
exactly 12 units.

Or:

The relative atomic mass of an element is the weighted average of

the masses of its isotopes relative to 1/12 of the mass of a carbon-12
atom.

A "weighted average" allows for the fact that there won't be equal amounts of the
various isotopes. This example should make that clear:
In chlorine, there are 3 atoms of chlorine-35 for every 1 of chlorine-37.
Suppose you had 4 typical atoms of chlorine.
The total mass of these would be (3 x 35) + (1 x 37) = 142
The average mass of these 4 atoms would be 142 / 4 = 35.5.
35.5 is the relative atomic mass of chlorine.
Notice the effect of the "weighted" average. A simple average of 35 and 37 is, of
course, 36. Our answer of 35.5 allows for the fact that there are more of the lighter
isotope of chlorine - and so the "weighted" average ought to be closer to that.
You can always find the relative atomic mass of an element from a Periodic Table.
But take care to choose the right number! Look at the key for the table, but, in any
case, the relative atomic mass will always be the larger number given in a periodic
element .

Relative molecular mass, Mr

You have to be careful with this term, because it should only be applied to
substances which actually exist as molecules. A molecule consists of a fixed number
of atoms joined together by covalent bonds. (Actually, in the case of the noble
gases, a molecule can also be a single atom.)
You shouldn't use the term for things, like sodium chloride, which are ionically
bonded.

Working out the relative molecular mass

You work out the relative molecular mass of a substance by adding up the
relative atomic masses of the atoms it consists of. So, for example, to work
out the relative molecular mass of water, H 2O, you add the relative atomic masses
of two hydrogens and one oxygen.
Mr of H2O = (2 x 1) + 16 = 18
To work out the relative molecular mass of CHCl 3:
Mr of CHCl3 = 12 + 1 + (3 x 35.5) = 119.5

Defining the relative molecular mass

Either:

The relative molecular mass of a substance is the weighted average of the

masses of the molecules on a scale on which a carbon-12 atom has a mass of
exactly 12 units.

Or:
The relative molecular mass of a substance is the weighted average

of the masses of the molecules relative to 1/12 of the mass of a

carbon-12 atom.

Note: You may find that many sources miss out the bit about weighted averages,
but this should be included unless you are thinking about the mass of a particular
molecule with a particular combination of isotopes of the various atoms.
For example, taking the example of CHCl3 above:
There is no single molecule of CHCl3 which has a mass of 119.5. The problem is that
an average sample of these molecules will contain isotopes of both chlorine-35 and
chlorine-37. That means that individual molecules can have the following masses:
12 + 1 + (3 x 35) = 118
12 + 1 + (2 x 35) + 37 = 120
12 + 1 + 35 + (2 x 37) = 122
12 + 1 + (3 x 37) = 124
The weighted average takes account of the proportions of each of these molecules
in an average sample of the substance.
Don't get too worried about all this! It is far more likely that you will have to work
out a relative molecular mass by adding up the relative atomic masses than that
you will have to define it.

Relative formula mass, Mr

Notice that relative formula mass is given exactly the same symbol, Mr, as relative
molecular mass.
In fact, relative formula mass is a much more useful term than relative molecular
mass because it includes everything, whatever the bonding. It works just as well for
ionic substances as for covalent substances.

I strongly recommend that you use this term all the time, and only talk
about relative molecular mass if you are specifically asked about it in an
exam.

Working out the relative formula mass

Write down the formula, and then add up all the relative atomic masses of the
atoms it contains.
Example 1
The relative formula mass of NaCl = 23 + 35.5 = 58.5
Example 2
The relative formula mass of copper(II) sulfate crystals, CuSO 4.5H2O:
Mr of CuSO4.5H2O = 63.5 + 32 + (4 x 16) + 5 x [(2 x 1) + 16] = 249.5

Be careful with things which contain water of crystallisation like the

copper(II) sulfate crystals in this example. Add the water up first and then multiply it
by 5 (or whatever other number you need). If you try to do it as hydrogen and
oxygen separately, you stand a good chance of getting it wrong. Students usually
remember to multiply the 2 hydrogens by 5, but forget to multiply the oxygen by 5.
If you add the water up as a whole, that can't happen.

Defining the relative formula mass

Either:

The relative formula mass of a substance is the weighted average of the

masses of the formula units on a scale on which a carbon-12 atom has a
mass of exactly 12 units.

Or:
The relative formula mass of a substance is the weighted average of

the masses of the formula units relative to 1/12 of the mass of a

carbon-12 atom.

The "formula unit" is just the formula as you have written it.

Learning outcome 1(b)

Working with moles

Working out the mass of a mole of a substance

Easy! Work out the relative formula mass, and then add the unit "grams".
Example 1: The mass of 1 mole of water, H2O
The relative formula mass of water, H2O = (2 x 1) + 16 =18
1 mole of water, H2O, weighs 18 g.

Example 2: The mass of 1 mole of sodium carbonate crystals, Na 2CO3.10H2O

The relative formula mass of sodium carbonate crystals, Na 2CO3.10H2O = (2 x 23) +
12 + (3 x 16) + 10 x [(2 x 1) + 16] = 286
1 mole of sodium carbonate crystals, Na2CO3.10H2O, weighs 286 g

The importance of quoting the formula

Whenever you talk about a mole of something you must quote the formula.
For example, if you were talking about a mole of sodium carbonate, you could mean
a mole of anhydrous sodium carbonate, Na2CO3, or a mole of the crystals,
Na2CO3.10H2O.
The mass of 1 mole of the anhydrous compound is 106 g; the mass of a mole of the
crystals is 286 g.
Or if you were talking about the mass of a mole of oxygen, you might be talking
about a mole of oxygen atoms, O, or a mole of oxygen molecules, O 2.
Always write down the formula you are referring to.

Converting between the mass of a substance and the number of moles

The formula is this:

So, if 1 mole of a substance weighs 40 g and you have 10 g of it, you have 10/40
moles - in other words you have 0.25 moles.
Incidentally, the abbreviation for moles which you would normally use in
calculations is mol.

If you had to work out other things, you could obviously rearrange this equation to
give:

and

What is the point of moles?

Defining a mole
Let's start with the hard bit, and define a mole.
A mole of substance is the amount of that substance that contains the same
number of stated elementary units as there are atoms in 12 g of carbon-12.
"Stated elementary units" could be any of the following examples:

chlorine atoms, Cl

chlorine molecules, Cl2

ammonia molecules, NH3

sodium chloride formula units, NaCl

and anything else that you care to write the formula of.
1 mole of any of these contains exactly the same number of the formula units you
have written - the same as the number of atoms in 12 g of the carbon-12 isotope
i.e. each mole pf a substance have same number of atoms called
the Avogadro Constant, and is given the symbol L.
The Avogadro Constant is a huge number (approximately 6.02 x 10 23). It has units of
mol-1, which you would read as "per mole".
In other words, there are 6.02 x 1023 of whatever formula units you are talking about
per mole of that formula.
So, in 18 g of water, H2O, there are 6.02 x 1023 water molecules.
In 58.5 g of sodium chloride, NaCl, there are 6.02 x 10 23 NaCl formula units.
In 2 g of hydrogen, H2, there are 6.02 x 1023 hydrogen molecules.
And so on, and so on . . .

So what?

Take a simple equation like:

How do you read this?

It could just be simply "Hydrogen and oxygen react to make water."
Or it could be "2 molecules of hydrogen and 1 molecule of oxygen react to make 2
molecules of water."
Moles enable you to do something much more useful. Notice that you need twice as
many molecules of hydrogen as you do of oxygen. If you had 1 mole of hydrogen
and 1 mole of oxygen, then they would contain the same number of molecules - the
Avogadro Constant.
So if you wanted to be sure that you were reacting twice as many molecules of
hydrogen as you had of oxygen, you would need twice as many moles.
That means that you can read the equation in a new way. The equation above could
say "2 moles of hydrogen react with 1 mole of oxygen to give 2 moles of water."
And that's why moles are so important. For calculation work, you can interpret
equations in terms of the number of moles of everything present - and you can then
go on to turn moles into actual masses of substances reacting.
For example, iron and sulfur react on heating to give iron(II) sulfide.

You can read that as "1 mole of iron, Fe, reacts with 1 mole of sulfur, S, to give 1
mole of iron(II) sulfide, FeS."
And by looking up the relative atomic masses, you find out that 56 g of iron will
react with 32 g of sulfur to give 88 g of iron(II) sulfide. That lets you know what
proportion to mix real iron and real sulfur together in, and how much product to
expect.
That's why moles are so important - they let you link equations to the actual
quantities of materials you are using.

Learning outcomes 1.3(a) and 1.3(b)

THE MASS SPECTROMETER

How a mass spectrometer works

The basic principle

If something is moving and you subject it to a sideways force, instead of moving in a

straight line, it will move in a curve - deflected out of its original path by the
sideways force.
Suppose you had a cannonball travelling past you and you wanted to deflect it as it
went by you. All you've got is a jet of water from a hose-pipe that you can squirt at
it. Frankly, its not going to make a lot of difference! Because the cannonball is so
heavy, it will hardly be deflected at all from its original course.
But suppose instead, you tried to deflect a table tennis ball travelling at the same
speed as the cannonball using the same jet of water. Because this ball is so light,
you will get a huge deflection.
The amount of deflection you will get for a given sideways force depends on the
mass of the ball. If you knew the speed of the ball and the size of the force, you
could calculate the mass of the ball if you knew what sort of curved path it was
deflected through. The less the deflection, the heavier the ball.

Note: I'm not suggesting that you personally would have to do the calculation,
although the maths isn't actually very difficult - certainly no more than A'level
standard!

You can apply exactly the same principle to atomic sized particles.

An outline of what happens in a mass spectrometer

Atoms and molecules can be deflected by magnetic fields - provided the atom or
molecule is first turned into an ion. Electrically charged particles are affected by a
magnetic field although electrically neutral ones aren't.
The sequence is :
Stage 1: Ionisation
The atom or molecule is ionised by knocking one or more electrons off to give a
positive ion. This is true even for things which you would normally expect to form
negative ions (chlorine, for example) or never form ions at all (argon, for example).
Most mass spectrometers work with positive ions.

Note: All mass spectrometers that you will come across if you are doing a course
for 16 - 18 year olds work with positive ions. Even if a few atoms in a sample of
chlorine, for example, captured an electron instead of losing one, the negative ions
formed wouldn't get all the way through the ordinary mass spectrometer. But it has

been pointed out to me that there is work being done on negative ion mass
spectrometers, although they use a different ionisation technique.

Stage 2: Acceleration
The ions are accelerated so that they all have the same kinetic energy.
Stage 3: Deflection
The ions are then deflected by a magnetic field according to their masses.
The lighter they are, the more they are deflected.
The amount of deflection also depends on the number of positive charges
on the ion - in other words, on how many electrons were knocked off in the
first stage. The more the ion is charged, the more it gets deflected.
i.e. amount of deflection the charge on the ion
Stage 4: Detection
The beam of ions passing through the machine is detected electrically.

A full diagram of a mass spectrometer

Understanding what's going on

The need for a vacuum

It's important that the ions produced in the ionisation chamber have a free run
through the machine without hitting air molecules.
Ionisation

The vaporised sample passes into the ionisation chamber. The electrically heated
metal coil gives off electrons which are attracted to the electron trap which is a
positively charged plate.
The particles in the sample (atoms or molecules) are therefore bombarded with a
stream of electrons, and some of the collisions are energetic enough to knock one
or more electrons out of the sample particles to make positive ions.
Most of the positive ions formed will carry a charge of +1 because it is much more
difficult to remove further electrons from an already positive ion.
These positive ions are persuaded out into the rest of the machine by the ion
repeller which is another metal plate carrying a slight positive charge.

Note: As you will see in a moment, the whole ionisation chamber is held at a
positive voltage of about 10,000 volts. Where we are talking about the two plates
having positive charges, these charges are in addition to that 10,000 volts.

Acceleration

The positive ions are repelled away from the very positive ionisation chamber and
pass through three slits, the final one of which is at 0 volts. The middle slit carries
some intermediate voltage. All the ions are accelerated into a finely focused beam.
Deflection

Different ions are deflected by the magnetic field by different amounts. The
amount of deflection depends on:
the mass of the ion. Lighter ions are deflected more than heavier

ones.
the charge on the ion. Ions with 2 (or more) positive charges are

deflected more than ones with only 1 positive charge.

These two factors are combined into the mass/charge ratio. Mass/charge
ratio is given the symbol m/z (or sometimes m/e).
For example, if an ion had a mass of 28 and a charge of 1+, its mass/charge ratio
would be 28. An ion with a mass of 56 and a charge of 2+ would also have a
mass/charge ratio of 28.
In the last diagram, ion stream A is most deflected - it will contain ions with
the smallest mass/charge ratio. Ion stream C is the least deflected - it
contains ions with the greatest mass/charge ratio.

It makes it simpler to talk about this if we assume that the charge on all the ions is
1+. Most of the ions passing through the mass spectrometer will have a charge of
1+, so that the mass/charge ratio will be the same as the mass of the ion.

Note: You must be aware of the possibility of 2+ (etc) ions, but the vast majority of
A'level questions will give you mass spectra which only involve 1+ ions. Unless
there is some hint in the question, you can reasonably assume that the ions you are
talking about will have a charge of 1+.

Assuming 1+ ions, stream A has the lightest ions, stream B the next lightest and
stream C the heaviest. Lighter ions are going to be more deflected than heavy ones.
Detection
Only ion stream B makes it right through the machine to the ion detector. The other
ions collide with the walls where they will pick up electrons and be neutralised.
Eventually, they get removed from the mass spectrometer by the vacuum pump.

When an ion hits the metal box, its charge is neutralised by an electron jumping
from the metal on to the ion (right hand diagram). That leaves a space amongst the
electrons in the metal, and the electrons in the wire shuffle along to fill it.
A flow of electrons in the wire is detected as an electric current which can be
amplified and recorded. The more ions arriving, the greater the current.
Detecting the other ions
How might the other ions be detected - those in streams A and C which have been
lost in the machine?
Remember that stream A was most deflected - it has the smallest value of m/z (the
lightest ions if the charge is 1+). To bring them on to the detector, you would need
to deflect them less - by using a smaller magnetic field (a smaller sideways force).

To bring those with a larger m/z value (the heavier ions if the charge is +1) on to the
detector you would have to deflect them more by using a larger magnetic field.
If you vary the magnetic field, you can bring each ion stream in turn on to the
detector to produce a current which is proportional to the number of ions arriving.
The mass of each ion being detected is related to the size of the magnetic field used
to bring it on to the detector. The machine can be calibrated to record current
(which is a measure of the number of ions) against m/z directly. The mass is
measured on the 12C scale.

Note: The

12

C scale is a scale on which the

12

C isotope weighs exactly 12 units.

What the mass spectrometer output looks like

The output from the chart recorder is usually simplified into a "stick diagram". This
shows the relative current produced by ions of varying mass/charge ratio.
The stick diagram for molybdenum looks lilke this:

You may find diagrams in which the vertical axis is labelled as either "relative
abundance" or "relative intensity". Whichever is used, it means the same thing. The
vertical scale is related to the current received by the chart recorder - and so to the
number of ions arriving at the detector: the greater the current, the more abundant
the ion.
As you will see from the diagram, the commonest ion has a mass/charge ratio of 98.
Other ions have mass/charge ratios of 92, 94, 95, 96, 97 and 100.
That means that molybdenum consists of 7 different isotopes. Assuming that the
ions all have a charge of 1+, that means that the masses of the 7 isotopes on the
carbon-12 scale are 92, 94, 95, 96, 97, 98 and 100.

Note: If there were also 2+ ions present, you would know because every
one of the lines in the stick diagram would have another line at exactly

half its m/z value (because, for example, 98/2 = 49). Those lines would be
much less tall than the 1+ ion lines because the chances of forming 2+
ions are much less than forming 1+ ions.

THE MASS SPECTRA OF ELEMENTS

This page looks at the information you can get from the mass spectrum of an
element. It shows how you can find out the masses and relative abundances of the
various isotopes of the element and use that information to calculate the relative
atomic mass of the element.
It also looks at the problems thrown up by elements with diatomic molecules - like
chlorine, Cl2.

The mass spectrum of monatomic elements

Monatomic elements include all those except for things like chlorine, Cl 2, with
molecules containing more than one atom.
The mass spectrum for boron

The number of isotopes

The two peaks in the mass spectrum shows that there are 2 isotopes of
boron - with relative isotopic masses of 10 and 11 on the 12C scale.

Notes: Isotopes are atoms of the same element (and so with the same number of
protons), but with different masses due to having different numbers of neutrons.
We are assuming (and shall do all through this page) that all the ions recorded have
a charge of 1+. That means that the mass/charge ratio (m/z) gives you the mass of
the isotope directly.
The carbon-12 scale is a scale on which the mass of the12C isotope weighs exactly
12 units.

The abundance of the isotopes

The relative sizes of the peaks gives you a direct measure of the relative
abundances of the isotopes. The tallest peak is often given an arbitrary height of
100 - but you may find all sorts of other scales used. It doesn't matter in the least.
You can find the relative abundances by measuring the lines on the stick diagram.
In this case, the two isotopes (with their relative abundances) are:
boron-10

23

boron-11

100

Working out the relative atomic mass

The relative atomic mass (RAM) of an element is given the symbol Ar and is defined
as:
The relative atomic mass of an element is the weighted average of the
masses of the isotopes on a scale on which a carbon-12 atom has a mass
of exactly 12 units.
A "weighted average" allows for the fact that there won't be equal amounts of the
various isotopes. The example coming up should make that clear.
Suppose you had 123 typical atoms of boron. 23 of these would be
would be 11B.

10

B and 100

The total mass of these would be (23 x 10) + (100 x 11) = 1330
The average mass of these 123 atoms would be 1330 / 123 = 10.8 (to 3
significant figures).
10.8 is the relative atomic mass of boron.
Notice the effect of the "weighted" average. A simple average of 10 and 11 is, of
course, 10.5. Our answer of 10.8 allows for the fact that there are a lot more of the
heavier isotope of boron - and so the "weighted" average ought to be closer to that.

The mass spectrum for zirconium

The number of isotopes

The 5 peaks in the mass spectrum shows that there are 5 isotopes of zirconium with relative isotopic masses of 90, 91, 92, 94 and 96 on the 12C scale.
The abundance of the isotopes
This time, the relative abundances are given as percentages. Again you can find
these relative abundances by measuring the lines on the stick diagram.
In this case, the 5 isotopes (with their relative percentage abundances) are:
zirconium-90

51.5

zirconium-91

11.2

zirconium-92

17.1

zirconium-94

17.4

zirconium-96

2.8

Note: You almost certainly wouldn't be able to measure these peaks to this degree
of accuracy, but your examiners may well give you the data in number form
anyway. We'll do the sum with the more accurate figures.

Working out the relative atomic mass

Suppose you had 100 typical atoms of zirconium. 51.5 of these would be
would be 91Zr and so on.

90

Zr, 11.2

Note: If you object to the idea of having 51.5 atoms or 11.2 atoms and so on, just
assume you've got 1000 atoms instead of 100. That way you will have 515 atoms,
112 atoms, etc. Most people don't get in a sweat over this, and just use the
numbers as they are!

The total mass of these 100 typical atoms would be

(51.5 x 90) + (11.2 x 91) + (17.1 x 92) + (17.4 x 94) + (2.8 x 96) = 9131.8
The average mass of these 100 atoms would be 9131.8 / 100 = 91.3 (to 3
significant figures).
91.3 is the relative atomic mass of zirconium.

The mass spectrum of chlorine

Chlorine is taken as typical of elements with more than one atom per molecule.
We'll look at its mass spectrum to show the sort of problems involved.
Chlorine has two isotopes, 35Cl and 37Cl, in the approximate ratio of 3 atoms of 35Cl
to 1 atom of 37Cl. You might suppose that the mass spectrum would look like this:

You would be wrong!

The problem is that chlorine consists of molecules, not individual atoms.
When chlorine is passed into the ionisation chamber, an electron is knocked off the
molecule to give a molecular ion,Cl2+. These ions won't be particularly stable, and
some will fall apart to give a chlorine atom and a Cl + ion. The term for this is
fragmentation.

If the Cl atom formed isn't then ionised in the ionisation chamber, it simply gets lost
in the machine - neither accelerated nor deflected.
The Cl+ ions will pass through the machine and will give lines at 35 and 37,
depending on the isotope and you would get exactly the pattern in the last diagram.
The problem is that you will also record lines for the unfragmented Cl2+ ions.
Think about the possible combinations of chlorine-35 and chlorine-37 atoms in a
Cl2+ ion.

Both atoms could be 35Cl, both atoms could be 37Cl, or you could have one of each
sort. That would give you total masses of the Cl 2+ ion of:
35 + 35 = 70
35 + 37 = 72
37 + 37 = 74
That means that you would get a set of lines in the m/z = 70 region looking like this:

These lines would be in addition to the lines at 35 and 37.

The relative heights of the 70, 72 and 74 lines are in the ratio 9:6:1.
What you can't do is make any predictions about the relative heights of the lines at
35/37 compared with those at 70/72/74. That depends on what proportion of the
molecular ions break up into fragments. That's why you've got the chlorine mass
spectrum in two separate bits so far. You must realise that the vertical scale in the
diagrams of the two parts of the spectrum isn't the same.
The overall mass spectrum looks like this:

Learning outcome 1.4(a)

This statement deals with the meaning of the words "empirical formula" and
"molecular formula".

Molecular formula

This can obviously only apply to

substances which consist of molecules - substances with a fixed
number of atoms joined together by covalent bonds.
(Or in the case of the noble gases, a molecule can also be a single
atom.)
The term "molecular formula" can't be applied to ionic substances like
sodium chloride.
The molecular formula of the hydrocarbon ethane is C 2H6, for example, and the
molecular formula of hydrogen peroxide is H 2O2.
The molecular formula gives a precise count of the numbers of each sort
of atom which make up the molecule.

Empirical formula
By contrast, the empirical formula tells you the simplest ratio of the various
atoms present in a substance. For example, in ethane (above) the ratio of the
number of carbon to hydrogen atoms is 1:3. The empirical formula is CH 3. For
hydrogen peroxide, where the simplest ratio is 1:1, the empirical formula is HO.
what is the point of them?
The empirical formulae for most molecular substances are virtually never used,
unless they happen to be the same as the molecular formula - as in H 2O, for
example. Or in other words unless both empirical formula and molecular
formulae are the same , the empirical formula is not always same as a
molecular formulae.
The word "empirical" means "derived from observation or experiment" - so
an empirical formula is one which you can find by doing experiments. In other
words, you can do an experiment which will tell you that the empirical formula of a
particular hydrocarbon (not ethane) is CH 2, for example.
That in itself isn't very helpful. The hydrocarbon could be C 2H4, C3H6, C4H8, and so on
and so on - anything with a carbon to hydrogen ratio of 1:2. To find out the correct
molecular formula from the empirical formula, you would have to do further
experiments.
The empirical formula is just a stage on the way to finding out the
molecular formula of something.
The empirical formula and ionic compounds
For ionic compounds, like sodium chloride, the formula quoted is almost
always the empirical formula.
In an ionic compound, there are no fixed numbers of ions - it depends on how big
the crystal is. So the formula of sodium chloride is simply given as NaCl, showing
the 1:1 ratio. The formula of sodium oxide is Na2O, showing a 2:1 ratio.

Exceptions:
Note: You may come across a few ionic compounds such as sodium peroxide,
Na2O2, or mercury(I) chloride, Hg2Cl2, where the formula normally used isn't the
empirical formula. There are good reasons for this which would be unnecessarily
confusing to discuss now. Almost all ionic compounds use the empirical formula with
the few exceptions.

In a real crystal of sodium chloride or sodium oxide, there will be some huge
variable number of positive and negative ions. The formula we write just tells us
what the ratio is.

Learning outcome 1.4(b)

This statement deals with how you work out empirical formulae and molecular
formulae from experimental data. It expects you to be able to do it in two ways from data about the masses or percentages of the various elements combined
together, or from data obtained from combustion experiments.
You also have to be able to work out a molecular formula from an empirical formula.
Finding empirical formulae from masses or percentages
If you have a formula like, say, CH4, you can read this as saying that 1 mole of
carbon atoms are combined with 4 moles of hydrogen atoms.
In a different example, if you could work out that phosphorus and oxygen atoms
combined together in the ratio of 2 moles of phosphorus atoms to 3 moles of
oxygen atoms, then you would know that the empirical formula was P 2O3.
You don't, of course know anything about the molecular formula. All you know is
that the ratio is 2:3. The molecular formula could equally well be P 4O6 or P6O9 or
whatever.
You can find mole ratios from data involving either the masses or percentages of the
combining atoms.

Finding empirical formulae from mass data

Suppose you found that 0.46 g of sodium formed 0.78 g of sodium sulfide. That
means that 0.46 g of sodium combines with (0.78 - 0.46) g = 0.32 g of sulfur.
It is clearest if you set your answer out as a simple table:
Na

mass

0.46 g

0.32 g

number of moles of atoms

0.46/23

0.32/32

= 0.02

= 0.01

ratio

That would tell you that the empirical formula was Na 2S.

Finding empirical formulae from percentage data

You might have been given the last example in a different form. You could have
been told that the compound contained 59.0% of Na and 41.0% of S by mass.
That's not a problem. If you had 100 g of the compound, then the masses of sodium
and sulfur would be 59.0 g and 41.0 g respectively. So use those figures in a sum
like the last one. Try it, and make sure you get the same answer as before.

Note: You may find that this time it isn't as easy to spot the ratio. If it isn't
immediately obvious, try dividing through by the smallest number. That will almost
invariably help.

Finding empirical formulae from combustion data

If you burn a compound containing carbon and hydrogen in an excess of air or
oxygen, carbon dioxide and water are formed. If you can trap the water and carbon
dioxide separately, you can find out what mass of each is formed. From that, you
can work out the empirical formula.
How you do this varies slightly depending on whether the compound contains
anything else as well as the carbon and hydrogen. We'll look at the two cases
separately.

If the compound only contains carbon and hydrogen

A compound which only contains carbon and hydrogen is called a hydrocarbon. Look
for this word in the question. You can only use this shorter method if you know that
there is nothing else present.

Here's an example:
When 0.78 g of a hydrocarbon was burned in excess air, 2.64 g of carbon dioxide
and 0.54 g of water were formed. Find the empirical formula of the hydrocarbon.
The important things to notice is that every mole of CO 2 contains 1 mole of carbon
atoms. Every mole of H2O contains 2 moles of hydrogen atoms.
1 mole of CO2 weighs 44 g.
No of moles of CO2 = 2.64/44 = 0.06
Therefore, no of moles of carbon atoms, C = 0.06
1 mole of H2O weighs 18 g.
No of moles of H2O = 0.54/18 = 0.03
Each mole of H2O contains 2 moles of hydrogen atoms.
Therefore, no of moles of hydrogen atoms, H = 0.06
The ratio of the number of moles of C : H is 1 : 1.
The empirical formula is CH.
It has taken several lines to write this down, but it is a simple calculation.

Note: If you are writing down a complete calculation rather than filling in answers
in a structured exam paper, it is important to include lots of words. Notice how
many words there are in the simple calculation above compared with the amount of
numbers. You have to include enough words to make it absolutely clear what you
are doing

If the compound contains other things as well as carbon

and hydrogen
This also applies to cases where you haven't been told that the compound is a
hydrocarbon. It might be a hydrocarbon, but you aren't sure.
The most likely cases you will come across will probably contain oxygen as well as
carbon and hydrogen.
In these cases, you have to put in extra steps in order to find out how much oxygen
(or whatever) is present. The sequence is:

Use the carbon dioxide figure to work out the number of moles of carbon
atoms.

From this, work out the mass of carbon present.

Use the water figure to work out the number of moles of hydrogen atoms.

From this, work out the mass of hydrogen present.

Add up the carbon and hydrogen masses, and compare them with the original
mass of compound. If there is no difference, then you have a hydrocarbon,
and the problem disappears. Just look at the ratio of the numbers of moles of
carbon and hydrogen atoms.

If there is a difference, assume the difference is due to oxygen unless you are told
differently. Work out the mass of oxygen present.

Find the number of moles of oxygen atoms present.

From the mole figures for carbon, hydrogen and oxygen, work out the
empirical formula.

This all seems a bit long-winded, but it is simple enough if you follow the stages
through in an example.
The question:
0.23 g of a compound containing carbon, hydrogen and possibly oxygen was burned
in an excess of air. 0.44 g of carbon dioxide and 0.27 g of water were formed. Work
out the empirical formula of the compound.
No of moles of CO2 = 0.44/44 = 0.01
Therefore, no of moles of carbon atoms, C = 0.01
and mass of carbon = 0.01 x 12 g = 0.12 g
No of moles of H2O = 0.27/18 = 0.015
Each mole of water contains 2 moles of hydrogen atoms.
Therefore, no of moles of hydrogen atoms, H = 2 x 0.015 = 0.03
and mass of hydrogen = 0.03 x 1 g = 0.03 g
Total mass of carbon and hydrogen in compound = 0.12 + 0.03 g = 0.15 g
Since you started with 0.23 g of compound, there is missing mass which must be
oxygen.
Mass of oxygen = 0.23 - 0.15 g = 0.08 g
No of moles of oxygen atoms, O = 0.08/16 = 0.005
The ratio of number of moles is C 0.01 : H 0.03 : O 0.005
Dividing through by the smallest number to give a simple ratio gives:
C2:H6:O1

The empirical formula is C2H6O.

Converting empirical formulae into molecular formulae

This is really simple! You can do it if you are told either the relative formula mass of
the compound or the mass of 1 mole (which is just the relative formula mass
expressed in grams).
Example 1
Let's follow on with the example above which resulted in an empirical formula of CH.
Suppose you knew that the relative formula mass was 78.
If you add up the relative formula mass of the empirical formula, CH, it comes to 12
+ 1 = 13.
The true molecular formula must be some multiple of this - so how many times does
13 go into 78?
Dividing 78 by 13 gives 6, and so the molecular formula must be 6 times bigger
than CH - in other words C6H6.
Example 2
And let's also follow on with the other example above which resulted in an empirical
formula of C2H6O. Suppose you knew that the mass of 1 mole was 46 g.
1 mole of the empirical formula, C2H6O, would have a mass of
(2 x 12) + (6 x 1) + 16 g = 46 g.
That's the same as the mass of 1 mole that you are given. Therefore the molecular
formula must be the same as the empirical formula - C 2H6O.

Learning outcome 3.1(a)

POints to remember

there are far more ions which don't have noble gas structures than
there are which do have noble gas structures.
the real reasons for the formation of a particular ion lie in the
energetics of the process.

IONIC (ELECTROVALENT) BONDING

This page explains what ionic (electrovalent) bonding is. It starts with a simple
picture of the formation of ions, and then modifies it slightly for A'level purposes.

A simple view of ionic bonding

The importance of noble gas structures
At a simple level (like GCSE) a lot of importance is attached to the electronic
structures of noble gases like neon or argon which have eight electrons in their
outer energy levels (or two in the case of helium). These noble gas structures are
thought of as being in some way a "desirable" thing for an atom to have.
You may well have been left with the strong impression that when other atoms
react, they try to organise things such that their outer levels are either completely
full or completely empty.

Note: The central role given to noble gas structures is very much an oversimplification. We shall have to spend some time later on demolishing the concept!

Ionic bonding in sodium chloride

Sodium (2,8,1) has 1 electron more than a stable noble gas structure (2,8). If it gave
away that electron it would become more stable.
Chlorine (2,8,7) has 1 electron short of a stable noble gas structure (2,8,8). If it
could gain an electron from somewhere it too would become more stable.
The answer is obvious. If a sodium atom gives an electron to a chlorine atom, both
become more stable.

The sodium has lost an electron, so it no longer has equal numbers of electrons and
protons. Because it has one more proton than electron, it has a charge of 1+. If
electrons are lost from an atom, positive ions are formed.
Positive ions are sometimes called cations.
The chlorine has gained an electron, so it now has one more electron than proton. It
therefore has a charge of 1-. If electrons are gained by an atom, negative ions are
formed.
A negative ion is sometimes called an anion.
The nature of the bond

The sodium ions and chloride ions are held together by the strong electrostatic
attractions between the positive and negative charges.
The formula of sodium chloride
You need one sodium atom to provide the extra electron for one chlorine atom, so
they combine together 1:1. The formula is therefore NaCl.

Some other examples of ionic bonding

magnesium oxide

Again, noble gas structures are formed, and the magnesium oxide is held
together by very strong attractions between the ions. The ionic bonding is
stronger than in sodium chloride because this time you have 2+ ions
attracting 2- ions. The greater the charge, the greater the attraction.
The formula of magnesium oxide is MgO.
calcium chloride

This time you need two chlorines to use up the two outer electrons in the calcium.
The formula of calcium chloride is therefore CaCl 2.
potassium oxide

Again, noble gas structures are formed. It takes two potassiums to supply the
electrons the oxygen needs. The formula of potassium oxide is K 2O.

THE A'LEVEL VIEW OF IONIC BONDING

Electrons are transferred from one atom to another resulting in the formation

of positive and negative ions.

The electrostatic attractions between the positive and negative ions hold the

compound together.
So what's new? At heart - nothing. What needs modifying is the view that there is
something magic about noble gas structures. There are far more ions which don't
have noble gas structures than there are which do.
Some common ions which don't have noble gas structures
You may have come across some of the following ions in a basic course like GCSE.
They are all perfectly stable , but not one of them has a noble gas structure.
Fe3+

[Ar]3d5

Cu2+

[Ar]3d9

Zn2+

[Ar]3d10

Ag+

[Kr]4d10

Pb2+

[Xe]4f145d106s2

Noble gases (apart from helium) have an outer electronic structure ns 2np6.
Apart from some elements at the beginning of a transition series
(scandium forming Sc3+ with an argon structure, for example), all
transition elements and any metals following a transition series (like tin
and lead in Group 4, for example) will have structures like those above.
That means that the only elements to form positive ions with noble gas structures
(apart from odd ones like scandium) are those in groups 1 and 2 of the Periodic
Table and aluminium in group 3 (boron in group 3 doesn't form ions).
Negative ions are tidier! Those elements in Groups 5, 6 and 7 which form simple
negative ions all have noble gas structures.
If elements aren't aiming for noble gas structures when they form ions, what
decides how many electrons are transferred? The answer lies in the energetics of
the process by which the compound is made.
What determines what the charge is on an ion?
Elements combine to make the compound which is as stable as possible - the one in
which the greatest amount of energy is evolved in its making. The more charges a
positive ion has, the greater the attraction towards its accompanying negative ion.
The greater the attraction, the more energy is released when the ions come
together.
That means that elements forming positive ions will tend to give away as many
electrons as possible. But there's a down-side to this.

Energy is needed to remove electrons from atoms. This is called ionisation

energy. The more electrons you remove, the greater the total ionisation energy
becomes. Eventually the total ionisation energy needed becomes so great that the
energy released when the attractions are set up between positive and negative ions
isn't large enough to cover it.
The element forms the ion which makes the compound most stable - the one in
which most energy is released over-all.
For example, why is calcium chloride CaCl2 rather than CaCl or CaCl3?
If one mole of CaCl (containing Ca + ions) is made from its elements, it is possible to
estimate that about 171 kJ of heat is evolved.
However, making CaCl2 (containing Ca2+ ions) releases more heat. You get 795 kJ.
That extra amount of heat evolved makes the compound more stable, which is why
you get CaCl2 rather than CaCl.
What about CaCl3 (containing Ca3+ ions)? To make one mole of this, you can
estimate that you would have to put in 1341 kJ. This makes this compound
completely non-viable. Why is so much heat needed to make CaCl3? It is
because the third ionisation energy (the energy needed to remove the third
electron) is extremely high (4940 kJ mol -1) because the electron is being removed
from the 3-level rather than the 4-level. Because it is much closer to the nucleus
than the first two electrons removed, it is going to be held much more strongly.

A similar sort of argument applies to the negative ion. For example, oxygen forms
an O2- ion rather than an O- ion or an O3- ion, because compounds containing the
O2- ion turn out to be the most energetically stable.