 The structure of ionic compounds

The positive metal ions and the negative ions produced when metals and non-metals react to form an ionic compound will be attracted to each other and pack as closely together as possible in a regular way. Structures with regular arrangements of atoms or ions are often referred to as being crystalline. The electrostatic attraction of positive and negative ions is called an ionic bond. Ionic compounds consist of a giant structure made of these ions. These giant structures of ions are often referred to as an ionic lattice. The smaller the ions and the more highly charged they are will mean that they can pack together more closely and form a stronger ionic bond. Sodium chloride is an ionic compound formed when sodium; a group I metal reacts with the halogen chlorine. Sodium will form an ion with a +1 charge. Chlorine a group 7 halogen will form an ion with a -1 charge. If you look at grains of sodium chloride, an ionic compound under the microscope you will see that they have a cubic shape. The image below shows the structure of the sodium chloride lattice. The green spheres represent chloride ions (Cl-) and the blue spheres sodium ions (Na+). Formula of an ionic compound If you were to count the ions in the model you would notice that there are equal numbers of sodium ions, Na+, and chloride ions, Cl-. This is simply because when the ions pack together they do in such a way that the charges always cancel out. The +1 charge on the sodium ion is cancelled out by the -1 charge on th chloride ion. So the ratio of the ions is 1:1. This simple ratio of ions enables you to calculate the empirical (simplest) formula for the compound. So in the case of sodium chloride it is NaCl. Its ionic formula is Na+Cl-.

You will often see the lattice structure for ionic compounds shown in different ways. This is to try and help you visualize what the giant structure looks like. Opposite is shown the cubic lattice for sodium chloride (Cl- shown in green, Na+ is a yellow/green colour), but this time there are bonds shown between the ions. In reality there would be no gaps between the ions as they will pack together as closely as possible but it does allow you to view the interior of the structure which is not possible from the first model. Both model allow you to visualize how the ions are arranged in the structure.

Co-ordination numbers None of the models for sodium chloride shown allow you to spot immediately how the crystal structure is built. If you pick out one sodium ion you should see that it has six immediate neighbours. One chloride above it and one below, one to its left and one to its right and one in front and one behind. This is shown opposite. The same is true if you pick a chloride ion. Each sodium or chloride ion has 6 immediate neighbours, the ions are described as 6 co-ordinate.

All ionic compounds have a giant lattice structure made up of ions. However not all ionic lattices have a face centred cubic structure like sodium chloride. Remember the ions will always try and pack together as closely as possible, but in a way that maximises the attraction between oppositely charged ions and reduces the repulsion between ions of a similar charge. However the different size of the ions in the compound will limit how closely they can pack together to maximise attractions and reduce repulsion.

Comparing sodium chloride and caesium chloride lattice structures. Caesium like sodium is an alkali metal, however caesium being in period 6 is a much larger atom than sodium. Caesium like sodium has one outer shell valency electron and so will form an ion with a 1+ charge, Cs+. This means that caesium chloride will have the formula CsCl where the caesium and chloride ions are in the ratio of 1:1, exactly the same as sodium chloride, NaCl. However caesium chloride has a different lattice structure from NaCl. The larger caesium ion allows 8 chloride ions to fit around it, that is its coordination number is 8, compared to 6 with sodium chloride. This is shown opposite:
Note that in the cell shown for both the NaCl and the CsCl lattice the metal ion is shown at the centre with the chloride ions surrounding it, to visualise the coordination number for chloride ion simply swap the position of the metal and the chloride ions around, put the chloride ion at the centre of the cell with the metal ions around it!

In caesium chloride you can visualise the caesium ions at the centre of a box with the chloride ions at the corner of this box. This type of structure is often referred to as body centred cubic (bcc). The coordination number for both the chloride and caesium ions is 8, this may be easier to visualise in the image below which shows a number of the CsCl cells that link to form part of the lattice structure for CsCl. The coordination number for each ion in the crystal must be the same since the ions are present in the ratio of 1:1. The image below shows ball and stick models for the structure of the calcium fluoride lattice. Clearly it is not cubic like the sodium chloride lattice because the ions are different in size and charge. In the models the red ions are Ca2+ and the blue ions are F-. What will be the empirical formula for calcium fluoride?

• calcium is a group II metal so has a 2+ charge. Ca2+
• fluoride is a group 7 non-metal, so has a 1- charge, F-
• We need to balance the charges, so will need 2 x F- ions to balance the 2+ charge on the calcium ion.
• So the empirical formula is CaF2

Group ions

Some ions are compounds and contain more than one type of element. You will have met these ions in the past but perhaps not realised they were group ions. For example the sulfate ion, SO42-, ammonium ion NH4+ and hydroxide ion OH- are all compounds and contain more than one element. These compounds are often called polyatomic ions or group ions. They are shown below: The formulae for the group ions you are likely to meet are given in the table below:
Group ion Elements present Charge Formula
hydroxide hydrogen, oxygen -1 OH-
nitrate nitrogen, oxygen 1- NO3-
sulfate sulfur, oxygen 2- SO42-
carbonate carbon, oxygen 2- CO32-
ammonium nitrogen, hydrogen 1+ NH4+
phosphate phosphorus, oxygen 3- PO43-

When working out the formula of compounds containing these ions we just use the same rules as before e.g.

What will be the formula for sodium sulfate?

 Ions present Symbol sodium sulfate Na SO42- 1 2 2 1 2 1 Na2SO4 The ionic formula is simply the formula with the charges on the ions present. The charges on the ions are simply the number of electrons lost or gained when the element reacts. This is the same as its valency and for group ions it is probably easiest if you simply memorise the formula for these ions! Na2+SO42-

Example 2: What is the formula for calcium nitrate?

 Ions present Symbol calcium nitrate Ca NO3- 2 1 1 2 1 2 Ca(NO3)2 When writing out the formula for calcium nitrate the calcium ions and nitrate ions are in the ratio of 1:2. The brackets are required around the nitrate simply because if they are omitted then we have NO32, which reads as 1 nitrogen and 32 oxygens, which is obviously not what we want. Ca(NO3)2-

Key Points

• Ionic compounds consist of a giant lattice structure composed of positively charged metal ions and negatively charged non-metal ions.
• An ionic bond is the attraction between a positively charged metal ion and a negatively charged non-metal ion.
• The empirical formula for an ionic compound will give you the ratio of the metal to non-metal ions in the structure.
• A crystalline structure is an ordered one, this means it is built up in a regular way e.g. you could for example describe a brick wall as crystalline, as the bricks are arranged in a regular and repeating pattern. If you knock the wall down and simply have a pile of bricks then this could be described as a non-crystalline arrangement or amorphous. Ionic compound have a giant crystalline lattice structure.