Born Haber Cycles part 2

The NaCl example in the previous part is very simple but covers most of what you need to know.

If they gave, for example, LiCl or KBr, the cycle would have exactly the same steps as they all involve a
metal 1+ ion and a non-metal 1- ion.

But they could give you something like MgCl2, which involves a Mg2+ ion and 2Cl-.

Steps
This time we are trying to get to Mg2+ and 2Cl- before we can do the lattice enthalpy.

There are a few differences with this cycle:

we need to do two ionisations of Mg.

as it is 2Cl- we are aiming for, we need 2 x the atomisation of Cl2 in the calculation.

we also need 2 x the first electron affinity of chlorine in the calculation. But isnt a second
electron affinity. Remember its still a 1- ion.
Calculation
Similarly to the NaCl example we can write out:

H2 + H3 + H4 + H5 + H6 + H7 = H1

Which rearranges to (assuming they ask for lattice enthalpy):

H7 = H1 (H2 + H3 + H4 + H5 + H6)

just remember to multiply H6 and H2 x 2.

Various combinations of ions

We have looked at the NaCl and MgCl2 examples. The common combinations of ions are:

+1 on the metal, -1 on the non-metal e.g. NaCl

+2 on the metal, -1 on the non-metal e.g. MgCl2

+1 on the metal, -2 on the non-metal e.g. Na2O

+2 on the metal, -2 on the non-metal e.g. CaO

Multiplying by 2

You need to make sure that you know when to multiply by 2.

you multiply by 2 when you have either 2+ and 1- or 1- and 2+

This was discussed briefly above in the MgCl2 above.

Another example is if you have Na2O, where there are 2Na+ and O2- ions. The Na atomisation and 1st
ionisation must be multiplied by 2. And you need the first and second electron affinities of oxygen but
you dont multiply those by 2.

when you are multiplying by 2 you always multiply by 2 twice. Atomisation and ionisation for metals
or atomisation and electron affinity for non-metals.
Lattice Enthalpy Theory
What affects lattice enthalpy?
A favourite question is to compare two ionic compounds and ask which will have the higher lattice
enthalpy.

Remember that lattice enthalpies are exothermic (a bond making process), so a high lattice enthalpy
means a highly exothermic value. It all comes down to size and charge on the ions:

the higher the charge higher lattice enthalpy

the smaller the ion higher lattice enthalpy

An ion with a high charge and a small size is said to have a high charge density.

A high charge density results in a strong electrostatic attraction between the positive and negative ion,
therefore forming a strong lattice and a lot of energy is released.

Both of these factors apply to both the positive and negative ion.

Example

MgO has a lattice enthalpy of -3791 kJ mol-1. Here we have Mg2+ and O2-.

MgCl2 has a lattice enthalpy of -2526 kJ mol-1. The ions are Mg2+ and Cl-.

NaCl is only -780 kJ mol-1. This time we have Na+ and Cl-.

You can see that the highest enthalpy (MgO) occurs for the ions with 2+ and 2- charges. Also, Mg is slightly
smaller than Na and O2- is smaller than Cl-.

Experimental v theoretical values

Quite often they will ask you why the lattice enthalpy that you calculated is different from the
experimental value.

The theoretical value is based on both ions being perfect spheres i.e. a perfect (100%) ionic compound.

But in reality, most ionic compounds are not 100% ionic. The positive ion polarises (pulls electrons away
from) the negative ion, which gives the compound some degree of covalent character. It is still an ionic
compound, but not 100% ionic.
When this occurs, the experimental and theoretical values start to differ in value.

the more polarisation that occurs, the greater the difference in the values

The rules:

the smaller the cation and the higher the charge more polarisation i.e. the cation has a high
charge density.

the larger the anion more polarisation i.e. it is easier to pull electrons away from it as it has a
low charge density.

The end result: the closer that the experimental and theoretical values are, then the closer to 100% ionic
character it has.