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Born-Haber Cycles part 1

Born-Haber Cycles
The aim with Born-Haber cycles is to work out the lattice enthalpy of an ionic compound (or another
enthalpy change). It is very similar to Hesss law but doesnt cause nearly as many problems.

The questions are normally in two parts:

a calculation/identifying enthalpy changes.

theory questions i.e. why two ionic compounds have different experimental and theoretical
enthalpy values.

Below is the Born-Haber cycle for the formation of NaCl. It might look complicated at first glance but
most students find it easier than Hesss Law as the steps and arrow directions dont change.

the direction of the arrows in the cycle tell you if the enthalpy change is exothermic or endothermic
i.e. of the point up it is endothermic and down is exothermic.

Enthalpy Changes
There are 5 types of enthalpy change in any Born Haber cycle: ionisation, atomisation, electron affinity,
lattice enthalpy and formation enthalpy.

Ionisation (endothermic)

You should know this one already!


Enthalpy change when one mole of gaseous ions are formed from 1 mole of gaseous atoms

Na(g) Na+(g) + e-

Atomisation (endothermic)

You probably havent seen this one before.

This involves the formation of an atom. It looks a bit strange seeing chlorine written as Cl rather than Cl2
but thats what happens.

Enthalpy change when one mole of gaseous ions is formed from an element in its standard state

Cl2(g) Cl(g)
Electron Affinity

You can think of this as the opposite of ionisation energy. We are adding an electron to a non-metal to
form a negative ion.

Enthalpy change when one mole of gaseous ions is formed from 1 mole of gaseous atoms

Cl(g) + e- Cl-(g)
If you are forming a 2- ion e.g. O2-, you need to do a second electron affinity.

the first electron affinity is exothermic but the second electron affinity is endothermic.

When adding a second electron, it is being added to a negative ion. Can you see the problem with that?
Electron repulsion! Therefore it takes energy to add that second electron resulting in an endothermic
process.

With the first electron affinity, the electron is being added to a neutral species so there is no problem.

Formation Enthalpy (exothermic)

You should know this one from Hesss law.

Enthalpy change when one mole of a compound is formed from the elements in their standard states

Na(s) + Cl2(g) NaCl(s)

Lattice Enthalpy (exothermic)

This goes back to ionic compounds that exist as ionic lattices.

You need a positive metal ion and a negative non-metal ion to form a lattice.
Enthalpy change when one mole of a solid compound is formed from the gaseous ions under standard
conditions

Na+(g) + Cl-(g) NaCl(s)

The Cycle
Start: the easiest place to start is from Na(s) + Cl2(g).

End: the end of the cycle is the formation of the ionic compound NaCl.

it is a good idea to have these start and end points in mind as it gives you an idea of where you are
trying to get to and can help you remember the enthalpy changes.

For example, you know that you need to get to Na+(g) and Cl-(g) before you can form the final product, this
means you have 1 atom of each ion and in the gas state (atomisation), you need a positive metal ion
(ionisation) and a negative metal ion (electron affinity).

There are two different routes to NaCl: one from the enthalpy of formation (the quick way) and the
other from the lattice enthalpy (the long way).

The enthalpy of formation is the shortest route but we cant measure this directly, so we need to use the
long route to. Exactly the same thing we did with Hesss law.

students often get the enthalpy of formation and lattice enthalpy mixed up. You need to get these
definitions clear as soon as possible, even if they are just in your own words.
you are unlikely to have to draw a complete cycle from nothing but it is a good exercise when
studying. If you can produce these diagrams without thinking too much then the questions will seem
very easy. It will also make you very familiar with the various enthalpy changes.

The order of the steps


We discussed the various definitions of the steps involved above. The diagram above shows the steps in a
certain order. However, you can change the order of the ionisation and atomisation steps. But you
cannot change the order of the electron affinity, lattice enthalpy or formation.

The order at that stage doesnt matter as long as you start with the elements in their standard states and
end up at the two ions in their gaseous states so you can do the lattice enthalpy.

sometimes in questions they might do two ionisations in one step or both atomisation steps.

Calculations
The calculations could ask you to work out a value for anby of the steps in the cycle, although frequently
it is the lattice enthalpy.

Using Hesss law theory, we add up all the arrows going in the same direction i.e. all the red arrows are
equal to the blue arrow, which gives us:

H2 + H3 + H4 + H5 + H6 = H1

I would recommend doing this every single time. I have see students try to rearrange too quickly or
others do something really difficult and reverse the sign of all the enthalpy changes. From experience
this just introduces problems. Keep it simple! Write it out in as many steps as you like as long as you
get it correct!

We can rearrange this to get H6 (the lattice enthalpy):

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

From there you just need to put in the numbers that they will give you in the questions.

another problem is when ions have a 2+ or 2- charge or have a 2 at the front, for example 2Cl-.
Students often dont know when to multiply by 2 or not. This is covered in the next part of the
tutorial.