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Haber Cycle part 2


The NaCl example is quite simple but covers most of what you need to know.
If they gave, for example, LiCl or KBr, it would be exactly the same except the numbers needed for the
calculation would change. All these examples involve a metal 1+ ion and a non-metal 1- ion so the steps
are all identical.
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 a first ionisation then a second ionisation of Mg.


as it is 2Cl- we are aiming for, we need 2 x the atomisation of Cl2.
we also need 2 x the first electron affinity of chlorine. It 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)

Various combinations of ions
We have looked at the NaCl and MgCl2 examples. It is worth noting the other possibilities that you could
have and what you need to do. You shouldnt get an example where the charge is greater than +2 or -2.
+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
You need to make sure that you know when to multiply by 2. You multiply by 2 when you have a +2 and -
1 or +1 and -2 combination. For example, see MgCl2 above. If you have Na2O, you will have 2Na+ and O2-
as the ions, so the Na atomisation and 1st ionisation must be multiplied by 2. And you need the first and
second electron affinities of oxygen.

Lattice Enthalpy Theory


Experimental v theoretical values
Another part that you need to know is how to answer theoretical lattice enthalpy questions.
Quite often they will ask you why the lattice enthalpy that you calculated is different from the
experimental value.
This all comes down to polarisation of ions (please see the tutorial on this if you are unsure).
The theoretical value is based on both ions being perfect spheres, which means that we are dealing with
a perfect ionic compound.
The positive ion polarises the negative ion, which starts to give the compound some degree of covalent
character. It is still an ionic compound, but with some degree of covalent bonding.
The rules:

the smaller the cation and the higher the charge more polarisation.
the larger the anion more polarisation (dont worry about charge on the anion, there appears
to be some debate as to the rule for this).

So the closer that the experimental and theoretical values match, then the less polarisation that occurs
i.e. the compound has a very high degree of ionic character.
What affects lattice enthalpy?
Another favourite is to compare two ionic compounds and ask which will have the higher lattice enthalpy.
So you need to know what affects lattice enthalpy.

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

the larger the charge higher lattice enthalpy


the smaller the ion higher lattice enthalpy

Both of these factors result in a stronger electrostatic attraction between the positive and negative ion,
therefore forming a stronger lattice and more energy is released.
For 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-.
AQA: they talk about the perfect ionic model. This just means that the two ions are perfect spheres
when 100% ionic.