IONIC STRUCTURES

This page explains the relationship between the arrangement of the

ions in a typical ionic solid like sodium chloride and its physical
properties - melting point, boiling point, brittleness, solubility and
electrical behaviour. It also explains why caesium chloride has a
different structure from sodium chloride even though sodium and
caesium are both in Group 1 of the Periodic Table.

The structure of a typical ionic solid - sodium chloride

How the ions are arranged in sodium chloride

Sodium chloride is taken as a typical ionic compound. Compounds

like this consist of a giant (endlessly repeating) lattice of ions. So
sodium chloride (and any other ionic compound) is described as
having a giant ionic structure.

You should be clear that giant in this context doesn't just mean
very large. It means that you can't state exactly how many ions
there are.

There could be billions of sodium ions and chloride ions packed

together, or trillions, or whatever - it simply depends how big the
crystal is. That is different from, say, a water molecule which
always contains exactly 2 hydrogen atoms and one oxygen atom -
never more and never less.

A small representative bit of a sodium chloride lattice looks like this:

If you look at the diagram carefully, you will see that the sodium
ions and chloride ions alternate with each other in each of the three
dimensions.

This diagram is easy enough to draw with a computer, but

extremely difficult to draw convincingly by hand. We normally draw
an "exploded" version which looks like this:
Only those ions joined by lines are actually touching each other.
The sodium ion in the centre is being touched by 6 chloride ions.
By chance we might just as well have centred the diagram around
a chloride ion - that, of course, would be touched by 6 sodium ions.
Sodium chloride is described as being 6:6-co-ordinated.

You must remember that this diagram represents only a tiny part of
the whole sodium chloride crystal. The pattern repeats in this way
over countless ions.

How to draw this structure

Draw a perfect square:

Now draw an identical square behind this one and offset a bit. You
might have to practice a bit to get the placement of the two squares
right. If you get it wrong, the ions get all tangled up with each other
in your final diagram.

Turn this into a perfect cube by joining the squares together:

Now the tricky bit! Subdivide this big cube into 8 small cubes by
joining the mid point of each edge to the mid point of the edge
opposite it. To complete the process you will also have to join the
mid point of each face (easily found once you've joined the edges)
to the mid point of the opposite face.

Now all you have to do is put the ions in. Use different colours or
different sizes for the two different ions, and don't forget a key. It
doesn't matter whether you end up with a sodium ion or a chloride
ion in the centre of the cube - all that matters is that they alternate
in all three dimensions.

You should be able to draw a perfectly adequate free-hand sketch

of this in under two minutes - less than one minute if you're not too
fussy!

Why is sodium chloride 6:6-co-ordinated?

The more attraction there is between the positive and negative

ions, the more energy is released. The more energy that is
released, the more energetically stable the structure becomes.

That means that to gain maximum stability, you need the maximum
number of attractions. So why does each ion surround itself with 6
ions of the opposite charge?

That represents the maximum number of chloride ions that you can
fit around a central sodium ion before the chloride ions start
touching each other. If they start touching, you introduce repulsions
into the crystal which makes it less stable.

The different structure of caesium chloride

We'll look first at the arrangement of the ions and then talk about
why the structures of sodium chloride and caesium chloride are
different afterwards.

How the ions are arranged in caesium chloride

Imagine a layer of chloride ions as shown below. The individual

chloride ions aren't touching each other. That's really important - if
they were touching, there would be repulsion.

Now let's place a similarly arranged layer of caesium ions on top of

these.

Notice that the caesium ions aren't touching each other either, but
that each caesium ion is resting on four chloride ions from the layer
below.

Now let's put another layer of chloride ions on, exactly the same as
the first layer. Again, the chloride ions in this layer are NOT
touching those in the bottom layer - otherwise you are introducing
repulsion. Since we are looking directly down on the structure, you
can't see the bottom layer of chloride ions any more, of course.

If you now think about a caesium ion sandwiched between the two
layers of chloride ions, it is touching four chloride ions in the bottom
layer, and another four in the top one. Each caesium ion is touched
by eight chloride ions. We say that it is 8-co-ordinated.

If we added another layer of caesium ions, you could similarly work

out that each chloride ion was touching eight caesium ions. The
chloride ions are also 8-co-ordinated.

Overall, then, caesium chloride is 8:8-co-ordinated.

The final diagram in this sequence takes a slightly tilted view of the
structure so that you can see how the layers build up. These
diagrams are quite difficult to draw without it looking as if ions of
the same charge are touching each other. They aren't!

Diagrams of ionic crystals are usually simplified to show the most

basic unit of the repeating pattern. For caesium chloride, you could,
for example, draw a simple diagram showing the arrangement of
the chloride ions around each caesium ion:

By reversing the colours (green chloride ion in the centre, and

orange caesium ions surrounding it), you would have an exactly
equivalent diagram for the arrangement of caesium ions around
each chloride ion.

Why are the caesium chloride and sodium chloride structures

different?

When attractions are set up between two ions of opposite charges,

energy is released. The more energy that can be released, the
more stable the system becomes. That means that the more
contact there is between negative and positive ions, the more
stable the crystal should become.

If you can surround a positive ion like caesium with eight chloride
ions rather than just six (and vice versa for the chloride ions), then
you should have a more stable crystal. So why doesn't sodium
chloride do the same thing?

Look again at the last diagram:

Now imagine what would happen if you replaced the caesium ion
with the smaller sodium ion. Sodium ions are, of course, smaller
than caesium ions because they have fewer layers of electrons
around them.

You still have to keep the chloride ions in contact with the sodium.
The effect of this would be that the whole arrangement would
shrink, bringing the chloride ions into contact with each other - and
that introduces repulsion.
Any gain in attractions because you have eight chlorides around
the sodium rather than six is more than countered by the new
repulsions between the chloride ions themselves. When sodium
chloride is 6:6-co-ordinated, there are no such repulsions - and so
that is the best way for it to organise itself.

Which structure a simple 1:1 compound like NaCl or CsCl

crystallises in depends on the radius ratio of the positive and the
negative ions. If the radius of the positive ion is bigger than 73% of
that of the negative ion, then 8:8-co-ordination is possible. Less
than that (down to 41%) then you get 6:6-co-ordination.

In CsCl, the caesium ion is about 93% of the size of the chloride
ion - so is easily within the range where 8:8-co-ordination is
possible. But with NaCl, the sodium ion is only about 52% of the
size of the chloride ion. That puts it in the range where you get 6:6-
co-ordination.

The physical properties of sodium chloride

Sodium chloride is taken as typical of ionic compounds, and is

chosen rather than, say, caesium chloride, because it is found on
every syllabus at this level.

Sodium chloride has a high melting and boiling point

There are strong electrostatic attractions between the positive and

negative ions, and it takes a lot of heat energy to overcome them.
Ionic substances all have high melting and boiling points.
Differences between ionic substances will depend on things like:

 The number of charges on the ions

Magnesium oxide has exactly the same structure as sodium

chloride, but a much higher melting and boiling point. The 2+
and 2- ions attract each other more strongly than 1+ attracts
1-.

 The sizes of the ions

If the ions are smaller they get closer together and so the
electrostatic attractions are greater. Rubidium iodide, for
example, melts and boils at slightly lower temperatures than
sodium chloride, because both rubidium and iodide ions are
bigger than sodium and chloride ions. The attractions are
less between the bigger ions and so less heat energy is
 needed to separate them.

Sodium chloride crystals are brittle

Brittleness is again typical of ionic substances. Imagine what

happens to the crystal if a stress is applied which shifts the ion
layers slightly.

Ions of the same charge are brought side-by-side and so the

crystal repels itself to pieces!

Sodium chloride is soluble in water

Many ionic solids are soluble in water - although not all. It depends
on whether there are big enough attractions between the water
molecules and the ions to overcome the attractions between the
ions themselves. Positive ions are attracted to the lone pairs on
water molecules and co-ordinate (dative covalent) bonds may form.
Water molecules form hydrogen bonds with negative ions.

Sodium chloride is insoluble in organic solvents

This is also typical of ionic solids. The attractions between

the solvent molecules and the ions aren't big enough to
overcome the attractions holding the crystal together.

The electrical behaviour of sodium chloride

Solid sodium chloride doesn't conduct electricity, because

there are no electrons which are free to move. When it
melts, sodium chloride undergoes electrolysis, which
involves conduction of electricity because of the movement
and discharge of the ions. In the process, sodium and
chlorine are produced. This is a chemical change rather
than a physical process.

The positive sodium ions move towards the negatively

charged electrode (the cathode). When they get there, each
sodium ion picks up an electron from the electrode to form
a sodium atom. These float to the top of the melt as molten
sodium metal. (And assuming you are doing this open to
the air, this immediately catches fire and burns with an
orange flame.)

The movement of electrons from the cathode onto the

sodium ions leaves spaces on the cathode. The power
source (the battery or whatever) moves electrons along the
wire in the external circuit to fill those spaces. That flow of
electrons would be seen as an electric current. (The
external circuit is all the rest of the circuit apart from the
molten sodium chloride.)

Meanwhile, chloride ions are attracted to the positive

electrode (the anode). When they get there, each chloride
ion loses an electron to the anode to form an atom. These
then pair up to make chlorine molecules. Chlorine gas is
produced. Overall, the change is . . .

The new electrons deposited on the anode are pumped off

around the external circuit by the power source, eventually
ending up on the cathode where they will be transferred to
sodium ions.

Molten sodium chloride conducts electricity because of the

movement of the ions in the melt, and the discharge of the
ions at the electrodes. Both of these have to happen if you
are to get electrons flowing in the external circuit.

In solid sodium chloride, of course, that ion movement can't

happen and that stops any possibility of any current flow in
the circuit.