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For sodium chloride, the solid is more stable than the gaseous
ions by 787 kJ mol-1, and that is a measure of the strength of the
attractions between the ions in the solid. Remember that energy (in
this case heat energy) is given out when bonds are made, and is
needed to break bonds.
So lattice enthalpy could be described in either of two ways.
You could describe it as the enthalpy change when 1 mole of
sodium chloride (or whatever) was formed from its scattered
gaseous ions. In other words, you are looking at a downward
arrow on the diagram.
In the sodium chloride case, that would be -787 kJ mol-1.
Or, you could describe it as the enthalpy change when 1
mole of sodium chloride (or whatever) is broken up to form
its scattered gaseous ions. In other words, you are looking at
an upward arrow on the diagram.
In the sodium chloride case, that would be +787 kJ mol-1.
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Both refer to the same enthalpy diagram, but one looks at it from
the point of view of making the lattice, and the other from the point
of view of breaking it up.
Unfortunately, both of these are often described as "lattice
enthalpy".
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You can see that the lattice enthalpy of magnesium oxide is much
greater than that of sodium chloride. That's because in magnesium
oxide, 2+ ions are attracting 2- ions; in sodium chloride, the
attraction is only between 1+ and 1- ions.
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Notice particularly that the "mol-1" is per mole of atoms formed NOT per mole of element that you start with. You will quite
commonly have to write fractions into the left-hand side of the
equation. Getting this wrong is a common mistake.
Born-Haber cycles
I am going to start by drawing a Born-Haber cycle for sodium
chloride, and then talk it through carefully afterwards. You will see
that I have arbitrarily decided to draw this for lattice formation
enthalpy. If you wanted to draw it for lattice dissociation enthalpy,
the red arrow would be reversed - pointing upwards.
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Focus to start with on the higher of the two thicker horizontal lines.
We are starting here with the elements sodium and chlorine in their
standard states. Notice that we only need half a mole of chlorine
gas in order to end up with 1 mole of NaCl.
The arrow pointing down from this to the lower thick line represents
the enthalpy change of formation of sodium chloride.
The Born-Haber cycle now imagines this formation of sodium
chloride as happening in a whole set of small changes, most of
which we know the enthalpy changes for - except, of course, for the
lattice enthalpy that we want to calculate.
The +107 is the atomisation enthalpy of sodium. We have to
produce gaseous atoms so that we can use the next stage in
the cycle.
The +496 is the first ionisation energy of sodium. Remember
that first ionisation energies go from gaseous atoms to
gaseous singly charged positive ions.
The +122 is the atomisation enthalpy of chlorine. Again, we
have to produce gaseous atoms so that we can use the next
stage in the cycle.
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Now we can use Hess's Law and find two different routes around
the diagram which we can equate.
As I have drawn it, the two routes are obvious. The diagram is set
up to provide two different routes between the thick lines.
So, here is the cycle again, with the calculation directly underneath
it . . .
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Find two routes around this without going against the flow of any
arrows. That's easy:
Hf = +148 + 738 + 122 - 349 - 753
Hf = -94 kJ mol-1
So the compound MgCl is definitely energetically more stable than
its elements.
I have drawn this cycle very roughly to scale, but that is going to
become more and more difficult as we look at the other two
possible formulae. So I am going to rewrite it as a table.
You can see from the diagram that the enthalpy change of
formation can be found just by adding up all the other numbers in
the cycle, and we can do this just as well in a table.
kJ
atomisation enthalpy of Mg
+148
1st IE of Mg
+738
atomisation enthalpy of Cl
+122
electron affinity of Cl
-349
lattice enthalpy
-753
calculated Hf
-94
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+148
1st IE of Mg
+738
2nd IE of Mg
+1451
atomisation enthalpy of Cl (x 2)
+244
electron affinity of Cl (x 2)
-698
lattice enthalpy
-2526
calculated Hf
-643
You can see that much more energy is released when you make
MgCl2 than when you make MgCl. Why is that?
You need to put in more energy to ionise the magnesium to give a
2+ ion, but a lot more energy is released as lattice enthalpy. That is
because there are stronger ionic attractions between 1- ions and
2+ ions than between the 1- and 1+ ions in MgCl.
So what about MgCl3? The lattice energy here would be even
greater.
So how does that change the numbers in the Born-Haber cycle this
time?
You need to add in the third ionisation energy of magnesium,
because you are making a 3+ ion.
You need to multiply the atomisation enthalpy of chlorine by
3, because you need 3 moles of gaseous chlorine atoms.
You need to multiply the electron affinity of chlorine by 3,
because you are making 3 moles of chloride ions.
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+148
1st IE of Mg
+738
2nd IE of Mg
+1451
3rd IE of Mg
+7733
atomisation enthalpy of Cl (x 3)
+366
electron affinity of Cl (x 3)
-1047
lattice enthalpy
-5440
calculated Hf
+3949
Conclusion
Magnesium chloride is MgCl2 because this is the combination of
magnesium and chlorine which produces the most energetically
stable compound - the one with the most negative enthalpy change
of formation.
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